Hot-melt pressure sensitive adhesive composition and method of application

Abstract

A hot-melt pressure sensitive adhesive (HMPSA) composition derived from renewable resources. The HMPSA composition contains an epoxidized oil, a nucleophilic compound, and a phenolic compound. The composition may be prepared through a thermal reaction process, resulting in a 100% solids material with excellent adhesive properties, as well as being manufactured using sustainable components, having a high bio-based materials content, having a high solids content, having a high bonding strength, and short curing times.

Description

[0001] Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0002] HOT-MELT PRESSURE SENSTIVE ADHESIVE COMPOSITION AND METHOD OF APPLICATION

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] The present application claims priority to U.S. Provisional Appl. No. 63 / 735,002, filed

[0005] December 17, 2024, the entire contents of which are incorporated herein by reference.

[0006] FIELD OF INVENTION

[0007] The present invention relates to a hot-melt pressure sensitive adhesive (HMPSA) composition derived from renewable sources. The present invention, in particular, relates to a pressure-sensitive adhesive sheet which includes a pressure-sensitive adhesive layer formed of the HMPSA composition. The HMPSA composition contains an epoxidized oil, a nucleophilic compound, and a phenolic compound. The composition may be prepared through a thermal reaction process, resulting in a 100% solids material with excellent adhesive properties. The adhesive composition of the present invention offers the advantage of, inter alia, being manufactured using sustainable components, having a high bio-based materials content, having a high solids content, having a high bonding strength, and short curing times.

[0008] BACKGROUND

[0009] Every day people are surrounded by and exposed to toxic glues and coatings. Conventional polyurethane based adhesive systems may be formed by reacting an isocyanate compound with a polyol compound, of which the polyol used may have at least one petroleumbased building block (such as ethylene oxide and / or propylene oxide). While such petrochemical based polyols are widely used, these polyols face many problems in addition to the health drawbacks, such as exhaustion of natural resources and fluctuations in price based on changes in oil price.

[0010] This is particularly problematic when considering hot-melt adhesives, which are commonly used in disposable products such as disposable diapers, feminine hygiene products, food packaging, and napkin. Pressure sensitive adhesives (PSAs) exist as a soft solid Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0011] (viscoelastic material) in a room temperature range and are designed to adhere easily to an adherend with pressure. PSAs are widely used in various applications, including labels, tapes, and medical devices.

[0012] Conventional PSAs and hot-melt pressure sensitive adhesives (HMPSAs) often rely on or incorporate petroleum-based resins, which have several drawbacks including environmental concerns and limited biodegradability. Considering that these products directly contact consumables or are in increasingly regulated markets, as well as ending up in landfills, significant attention is placed on finding safe, cost-effective solutions.

[0013] Although bio-based oils may seem to be an attractive alternative, most bio-based oils are not miscible in water and therefore these alternatives typically contain volatile organic compounds and / or strong off-gassing odors. There is a growing need for sustainable and biobased alternatives that offer comparable performance.

[0014] SUMMARY

[0015] Provided is a hot-melt pressure sensitive adhesive composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound dissolved in a solvent.

[0016] In an embodiment of the present invention, the epoxidized oil is an epoxidized soybean oil.

[0017] In an embodiment of the present invention, the nucleophilic compound is malic acid.

[0018] In an embodiment of the present invention, the phenolic compound is tannic acid.

[0019] In an embodiment of the present invention, the solvent is water.

[0020] Provided is a method of making a hot-melt pressure sensitive adhesive composition comprising:

[0021] (a) Mixing (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound,

[0022] (b) Thermally reacting the mixture in (a) for a time and under conditions sufficient to form a HMPSA composition, and Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0023] (c) Cooling the HMPSA composition.

[0024] Provided is a pressure-sensitive adhesive sheet with at least one hot-melt pressure sensitive adhesive layer comprising a hot-melt pressure sensitive adhesive composition on a substrate, wherein the hot-melt pressure sensitive adhesive composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound.

[0025] Provided is method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:

[0026] (a) Applying a hot-melt pressure sensitive (HMPSA) composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic,

[0027] (b) Heating the HMPSA composition to a temperature sufficient to reactivate the HMPSA composition,

[0028] (c) Contacting the surface of the first material to the surface of the second surface, and

[0029] (d) Allowing the HMPSA composition to cool to ambient temperature.

[0030] Provided is a method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:

[0031] (a) Removing a release-treated sheet or release liner from a pressure-sensitive (PSA) sheet comprising a hot-melt pressure sensitive adhesive (HMPSA) composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound to expose the HMPSA composition,

[0032] (b) Applying the PSA sheet to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic, and Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0033] (c) Contacting the surface of the first material to the surface of the second surface.

[0034] DETAILED DESCRIPTION

[0035] Unless specifically defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled artisan in chemistry (e.g., polyurethane chemistry), coatings, and adhesives.

[0036] All methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, with suitable methods and materials being described herein. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and are not intended to be limiting, unless otherwise specified.

[0037] Reference will now be made in detail to each embodiment of the present invention. Such embodiments are provided by way of explanation of the present invention, which is not intended to be limited thereto. In fact, those of ordinary skill in the art may appreciate upon reading the present specification and viewing the present drawings that various modifications and variations can be made thereto.

[0038] For clarity, the terms " adhesive", "adhesive composition", and "HMPSA composition" are used interchangeably herein unless stated otherwise. For clarity, the “HMPSA composition” corresponds to a form of the composition which is used in a hot melt (thermal fusion) form at the time of forming the PSA layer. Once the PSA layer is formed, the present application utilizes the terms “HMPSA” or “HMPSA layer”.

[0039] The present disclosure provides a HMPSA composition containing (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound. The phenolic compound may be pre-blended with a solvent. In a particular embodiment, the HMPSA composition is a reaction product of an epoxidized soybean oil, malic acid, and tannic acid (which has been preblended with water).

[0040] The present disclosure provides a pressure-sensitive adhesive sheet with at least one Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0041] HMPSA layer on a substrate.

[0042] The present disclosure also provides methods of making a HMPSA composition, a method of making a HMPSA sheet, and methods of using a pressure-sensitive adhesive sheet containing at least one HMPSA layer on a substrate.

[0043] (A) Epoxidized Oil

[0044] The epoxidized oil may be derived from a synthetic and / or natural oil.

[0045] In an embodiment, the epoxidized oil can be any suitable epoxidized oil obtained from a sustainable source. The sustainable source can be a plant oil, vegetable oil, tree oil, nut oil, or animal oil.

[0046] In an embodiment, the oil is epoxidized using a suitable epoxidation agent, such as a peracid (e.g., peracetic acid) or m-chloroperoxybenzoic acid, to introduce epoxy groups into the triglyceride structure. The epoxidized oil can also be obtained by a simple reaction of a suitable oil with acid and hydrogen peroxide can yield epoxidized oil. A perester may also be used to form an epoxidized oil.

[0047] The epoxidized oil can be a sustainable and / or natural oil (e.g., an oil derived from a plant, vegetable, tree, nut, or animal).

[0048] Epoxidation can be of a subject oil or an oil that has been synthetically or enzymatically modified to incorporate one or more non-conjugated carbon-carbon double bonds.

[0049] Non-limiting examples of oils that can be directly epoxidized include oils that have one or more non-conjugated carbon-carbon double bonds (i.e., an unsaturated fatty acid), two or more non-conjugated carbon-carbon double bonds, three or more non-conjugated carboncarbon double bonds, four or more non-conjugated carbon-carbon double bonds, five or more non-conjugated carbon-carbon double bonds, six or more non-conjugated carbon-carbon double bonds, seven or more non-conjugated carbon-carbon double bonds, eight or more nonconjugated carbon-carbon double bonds, nine or more non-conjugated carbon-carbon double bonds, or ten or more non-conjugated carbon-carbon double bonds. As an upper limit to any of the foregoing ranges, twenty or less non-conjugated carbon-carbon double bonds, fifteen or less non-conjugated carbon-carbon double bonds, twelve or less non-conjugated carbon-carbon double bonds, ten or less non-conjugated carbon-carbon double bonds, nine or less non Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) conjugated carbon-carbon double bonds, eight or less non-conjugated carbon-carbon double bonds, seven or less non-conjugated carbon-carbon double bonds, six or less non-conjugated carbon-carbon double bonds, five or less non-conjugated carbon-carbon double bonds, four or less non-conjugated carbon-carbon double bonds, three or less non-conjugated carbon-carbon double bonds, or two or less non-conjugated carbon-carbon double bonds are envisioned. As such, envisioned are ranges of the foregoing where a lower limit and an upper limit are selected as illustrated by the following exemplary ranges one to ten non-conjugated carbon-carbon double bonds, one to eight non-conjugated carbon-carbon double bonds, one to six nonconjugated carbon-carbon double bonds, one to four non-conjugated carbon-carbon double bonds, one to three non-conjugated carbon-carbon double bonds, two to ten non-conjugated carbon-carbon double bonds, two to eight non-conjugated carbon-carbon double bonds, two to six non-conjugated carbon-carbon double bonds, two to four non-conjugated carbon-carbon double bonds, two to three non-conjugated carbon-carbon double bonds, three to ten nonconjugated carbon-carbon double bonds, three to eight non-conjugated carbon-carbon double bonds, three to six non-conjugated carbon-carbon double bonds, three to four non-conjugated carbon-carbon double bonds, four to ten non-conjugated carbon-carbon double bonds, four to eight non-conjugated carbon-carbon double bonds, and four to six non-conjugated carboncarbon double bonds.

[0050] In an embodiment of the present invention, prior to epoxidation, a subject oil can be subjected to a dehydrogenation (i.e., desaturation) reaction to introduce one or more nonconjugated carbon-carbon double bonds into one more carboxylic chain of a constituent saturated fatty acid. Exemplary reactions of forming an unsaturated fatty acid are direct desaturation utilizing oxygen and NADPH, selective desaturation using a fatty acid desaturase, or anaerobic arrangement. In an embodiment of the present invention, desaturation conditions are controlled to engineer an oil having the foregoing number(s) of non-conjugated carboncarbon double bonds.

[0051] In an embodiment of the present invention, the oil that can be epoxidized (directly or after dehydrogenation) is almond oil, avocado oil, bay oil, basil oil, bergamot oil, oils derived from biomass, Brazil nut oil, broccoli oil, cade oil, canola oil, caraway seed oil, cashew oil, cashew nutshell liquid, cinnamon leaf oil, citronella java oil, citrus seed oil, cod liver oil, com oil, cocoa butter, cottonseed oil, cumin oil, cypress oil, fish oil, flaxseed oil, geranium oil, grapefruit oil, hazelnut oil, lavender oil, lemongrass oil, linseed oil, macadamia nut oil, mandarin oil, melissa oil, myrtle oil, neem oil, nutmeg oil, oat oil, olive oil, palm oil, palmarosa Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) oil, peanut oil, pecan oil, peppermint oil, pine nut oil, pistachio oil, rapeseed oil, safflower oil, sage oil, sesame oil, soybean oil, spearmint oil, sunflower oil, high oleic sunflower oil, tea tree oil, thyme oil, triolein, vegetable oil, Vernonia oil, vetiver Haiti oil, walnut oil, wormwood oil, ylang ylang oil or any combination of two or more of the foregoing oils.

[0052] The degree of epoxidation of the foregoing oil may be partial (at least 10%, at least 20%, at least 25%, at least 30%, at least 33%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 90%, or at least 95%) or complete (100%) of the nonconjugated carbon-carbon double bonds. The foregoing percentages are understood to be average degrees of epoxidation across all epoxidized oils present in the HMPSA composition. For example, in an embodiment of the present invention two or more forms of the same or of different base epoxidized oils can be present in the HMPSA composition and, when present, the average degree of epoxidation meets the foregoing ranges.

[0053] Thus, in an embodiment of the present invention, the HMPSA composition comprises two or more epoxidized oils of the same (differ by degree of epoxidation) or different (differ by type and / or degree of epoxidation) base oil and, optionally, one or more oil of the same or different type that has not been epoxidized (i.e., 0% epoxidation). Where the epoxidized oil is mixed with an oil of the same or different type that has not been epoxidized, the ratio of the oils is such that the final average degree of epoxidation is at least 10%, at least 20%, at least 25%, at least 30%, at least 33%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 90%, or at least 95%. In an embodiment of the present invention, the total amount of non-epoxidized oil does not exceed 60% by weight, does not exceed 55%, does not exceed 50%, does not exceed 45%, does not exceed 40%, does not exceed 35%, does not exceed 30%, does not exceed 25%, does not exceed 20%, does not exceed 15%, or does not exceed 10% of the total amount of oil present in the HMPSA composition.

[0054] The epoxidized oil of the present invention will have at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten epoxy groups. As an upper limit to any of the foregoing ranges, twenty or less, fifteen or less, twelve or less, ten or less, nine or less, eight or less, seven or less, six or less, five or less, four or less, three or less, or two or less epoxy groups are envisioned. As such, envisioned are ranges of the foregoing where a lower limit and an upper limit are selected as illustrated by the following exemplary ranges one to ten, one to eight, one to six, one to four, one to three, two to ten, two to eight, two to six, two to four, two to three, three to ten, three to eight, three to six, Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) three to four, four to ten, four to eight, and four to six epoxy groups. The epoxy groups may be internal or terminal epoxy groups.

[0055] In an embodiment of the present invention, the epoxidized oil has a viscosity of 100 to 1000 cps at 25°C, 200 to 800 cps at 25°C, 300 to 700 cps at 25°C, 400 to 650 cps at 25°C, and 450 to 550 cps at 25°C.

[0056] In an embodiment, the epoxidized oil is epoxidized soybean oil. An exemplary structure of the epoxidized soybean oil is as follows:

[0057] (B) Nucleophilic compound

[0058] The nucleophilic compound may be any suitable nucleophile that is sufficiently nucleophilic to open an epoxy ring on the epoxidized oil. The nucleophilic compound may be natural or synthetic.

[0059] In an embodiment of the present invention, the nucleophilic compound contains at least two reactive functional groups (i.e., a multi-functional nucleophile) to permit crosslinking reactions with the epoxidized oil. Nucleophilic compounds include amine-containing compounds, amide-containing compounds, hydroxyl-containing compounds, and sulfhydryl- containing compounds. In an embodiment of the present invention, the nucleophilic compound contains one or more nucleophilic atoms selected from halides, oxygen, nitrogen, and sulfur and / or nucleophilic functional groups selected from water, alcohols, phenols, amines, thiols, and carboxylates. General examples, include halides (fluoride, chloride, bromide, iodide), azides, hydroxide, cyanide, thiol, ammonia, and water.

[0060] Non-limiting examples of the nucleophilic compound includes malic acid, glycerol, adipic acid, azelaic acid, dodecanoic acid, maleic acid, itaconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, fumaric acid and succinic acid, or a combination of two Attomey Docket No. 40787 / 65 (BIOB- 18 / 01WO) or more of the foregoing.

[0061] In an embodiment of the present invention, the nucleophilic compound is glycerol.

[0062] In an embodiment of the present invention, the nucleophilic compound is malic acid.

[0063] (C) Phenolic compound

[0064] As noted above, the HMPSA composition further comprises a phenolic compound which may serve as an HMPSA promoter. In certain embodiments, the HMPSA composition can comprise one or more different phenolic compounds.

[0065] The term "phenolic compound" refers to a compound with a chemical structure that has at least one aromatic ring with one or more hydroxyl groups attached to the aromatic ring. The "phenolic compound" may also include polyphenol, which may have more than one aromatic ring with one or more hydroxyl groups attached to the more than one aromatic ring. For example, the phenolic compound in accordance with the present invention may be a monocyclic or bicyclic aryl group having one or more hydroxyl-substituents. The phenolic compound can also include polyphenols. An example of a polyphenol is a compound having more than one aromatic group which may be fused rings or separated by a linking group or a direct bond and which has at least one hydroxyl substituent on one or more aromatic rings including one, multiple, or all aromatic rings.

[0066] Exemplary phenolic compounds include monophenols (such as, for example, phenol, cresol, guaiacol, apiole, carnosol, carvacrol, xylenol, dillapiole, eugenol, rosemarinol, capsaicin, methyl salicylate, butylated hydroxytoluene, 4-nonylphenol, tyrosine, thymol, raspberry ketone, orthophenyl phenol); phenols containing multiple hydroxyl groups (such as, for example, gallol, pyrogallol, bisphenol A); phenols containing multiple fused rings (such as, for example, juglone, estradiol, sesamol, serotonin); phenolic aldehydes (such as, for example, 3,4-dihydroxybenzadehyde); flavonoids (polyphenols) including flavonols (such as, for example, quercetin, fingerol, kaempferol, myricetin, rutin, isorhamnetin), flavanones (such as, for example, fesperidin, naringenin, silybin, eriodictyol), flavones (such as, for example, apigenin, tangeritin, luteolin), flavan-3-ols (such as, for example, catechins, (+)-catechin, (+)- gallocatechin, (-)-epicate chin, (-)-epigallocatechin, (-)-epigallocatechin gallate (EGCG), (-)- epicatechin 3-gallate, theaflavin, theaflavin-3-gallate, theaflavin-3 '-gallate, theaflavin-3,3'- Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) digallate, thearubigins), anthocyanins (flavonals) and anthocyanidins (such as, for example, pelargonidin, peonidin, cyanidin, delphinidin, malvidin, petunidin), isoflavones (phytoestrogens) (such as, for example, daidzein (formononetin), genistein (biochanin A), glycitein), dihydroflavonols, chaicones, coumestans (phytoestrogens), and coumestrol; Phenolic acids (such as: ellagic acid, gallic acid, tannic acid, 3,4-dihydroxybenzoic acid, picric acid, salicylic acid, vanillin, curcumin); hydroxycinnamic acids (such as, for example, caffeic acid, chlorogenic acid, cinnamic acid, ferulic acid, coumarin); lignans (phytoestrogens), silymarin, secoisolariciresinol, pinoresinol and lariciresinol); tyrosol esters (such as, for example, tyrosol, hydroxytyrosol, oleocanthal, oleuropein); stilbenoids (such as, for example, resveratrol, pterostilbene, piceatannol) and punicalagins; and complex polyphenols (such as, for example, lignin), or a combination of two or more of the foregoing.

[0067] In an embodiment of the present invention, the phenolic compound can be selected from catechol, vanillin, gallic acid, caffeic acid, juglone, gallol, lignin, tannic acid, 3,4- dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, quercitin, (+) catechin hydrate, or comprise any combination of two or more of the foregoing.

[0068] In an embodiment of the present invention, the phenolic compound comprises at least one catechol group of the following structure:

[0069] In an embodiment of the present invention, the phenolic compound comprises a gallic acid comprising the following chemical structure:

[0070] In an embodiment of the present invention, the phenolic compound comprises tannic acid comprising the following chemical structure: Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0071] Tannic acid comprises reactive terminal phenolic hydroxyl groups with a hyperbranched aromatic / alicyclic polyester core, which can form highly cross-linked networks with the epoxy groups of the epoxidized oil. Thus, tannic acid may be used as the sole phenolic compound whereas in other embodiments a blend of phenolic compounds may be advantageous.

[0072] In an embodiment of the present invention, the phenolic compound is pre-blended with a solvent to tune and / or optimize the adhesion properties of the HMPSA composition. The use of a solvent may also help in the dissolution and incorporation of the phenolic compound. Thus, the solvent is added in a pre-blending step prior to the reaction. In some embodiments, the HMPSA composition further comprises a solvent when the phenolic compound used is tannic acid.

[0073] Any suitable solvent that solubilizes the phenolic compound can be used. Examples of the solvent include, but are not limited to, alcohols such as ethanol or methanol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide. The solvent used has low or no VOCs.

[0074] In an embodiment of the present invention, a solvent is included in the HMPSA composition and the solvent is water.

[0075] In an embodiment of the present invention, the amount of solvent to be utilized is only Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) the amount required to fully dissolve the phenolic compound. Exemplary amounts include the formation of a composition of phenolic compound(s) in solvent at a concentration of at least 0.001 g / mL, at least 0.01 g / mL, at least 0.05 g / ml, at least 0.075 g / ml, at least 0.1 g / ml, at least 0.15 g / ml, at least 0.2 g / ml, at least 0.25 g / ml, at least 0.3 g / ml, at least 0.35 g / ml, at least 0.4 g / ml, at least 0.45 g / ml, at least 0.5 g / ml, at least 0.55 g / ml, at least 0.6 g / ml, at least 0.65 g / ml, at least 0.7 g / ml, at least 0.75 g / ml, at least 0.8 g / ml, at least 0.85 g / ml, at least 0.9 g / ml, at least 0.95 g / ml, or at least 1 g / ml. As an upper limit, exemplary amounts include the formation of a composition of phenolic compound(s) in solvent at a concentration of at most 2 g / ml, at most 1.75 g / ml, at most 1.5 g / ml, at most 1.25 g / ml, at most 1 g / ml, at most 0.95 g / ml, at most 0.9 g / ml, at most 0.85 g / ml, at most 0.8 g / ml, at most 0.75 g / ml, at most 0.7 g / ml, at most 0.65 g / ml, at most 0.6 g / ml, at most 0.55 g / ml, or at most 0.5 g / ml. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 0.001 g / mL to 2 g / ml, 0.01 g / mL to 2 g / ml, 0.05 g / mL to 2 g / ml, 0.1 g / mL to 2 g / ml, 0.2 g / mL to 2 g / ml, 0.25 g / mL to 2 g / ml, 0.3 g / mL to 2 g / ml, 0.35 g / mL to 2 g / ml, 0.4 g / mL to 2 g / ml, 0.45 g / mL to 2 g / ml, 0.5 g / mL to 2 g / ml, 0.55 g / mL to 2 g / ml, 0.6 g / mL to 2 g / ml, 0.65 g / mL to 2 g / ml, 0.7 g / mL to 2 g / ml, 0.75 g / mL to 2 g / ml, 0.001 g / mL to 1.5 g / ml, 0.01 g / mL to 1.5 g / ml, 0.05 g / mL to 1.5 g / ml, 0.1 g / mL to 1.5 g / ml, 0.2 g / mL to 1.5 g / ml, 0.25 g / mL to 1.5 g / ml, 0.3 g / mL to 1.5 g / ml, 0.35 g / mL to 1.5 g / ml, 0.4 g / mL to 1.5 g / ml, 0.45 g / mL to 1.5 g / ml, 0.5 g / mL to 1.5 g / ml, 0.55 g / mL to 1.5 g / ml, 0.6 g / mL to 1.5 g / ml, 0.65 g / mL to 1.5 g / ml, 0.7 g / mL to 1.5 g / ml, 0.75 g / mL to 1.5 g / ml, 0.001 g / mL to 1 g / ml, 0.01 g / mL to 1 g / ml, 0.05 g / mL to 1 g / ml, 0.1 g / mL to 1 g / ml, 0.2 g / mL to 1 g / ml, 0.25 g / mL to 1 g / ml, 0.3 g / mL to 1 g / ml, 0.35 g / mL to 1 g / ml, 0.4 g / mL to 1 g / ml, 0.45 g / mL to 1 g / ml, 0.5 g / mL to 1 g / ml, 0.55 g / mL to 1 g / ml, 0.6 g / mL to 1 g / ml, 0.65 g / mL to 1 g / ml, 0.7 g / mL to 1 g / ml, 0.75 g / mL to 1 g / ml, 0.001 g / mL to 0.75 g / ml,

[0076] 0.01 g / mL to 0.75 g / ml, 0.05 g / mL to 0.75 g / ml, 0.1 g / mL to 0.75 g / ml, 0.2 g / mL to 0.75 g / ml,

[0077] 0.25 g / mL to 0.75 g / ml, 0.3 g / mL to 0.75 g / ml, 0.35 g / mL to 0.75 g / ml, 0.4 g / mL to 0.75 g / ml,

[0078] 0.45 g / mL to 0.75 g / ml, 0.5 g / mL to 0.75 g / ml, 0.55 g / mL to 0.75 g / ml, 0.6 g / mL to 0.75 g / ml, and 0.65 g / mL to 0.75 g / ml.

[0079] Further, in an embodiment of present the invention, the solvent and any residual water is removed from the HMPSA composition by evaporation, vacuum, or any other suitable methodology during or after the reaction step. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0080] Hot-melt pressure sensitive adhesive composition content ratios and amounts

[0081] In an embodiment of the present invention, the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0. l-10):(0. l-10):(0. 1-10). Exemplary as ratios include: (0.2-9.5):(0.2-9.5):(0.2-9.5), (0.3-9):(0.3-9):(0.3-9), (0.4-8.5):(0.4-8.5):(0.4-

[0082] 8.5), (0.5-8):(0.5-8):(0.5-8), (0.6-7.5):(0.6-7.5):(0.6-7.5), (0.7 -7):(0.7 -7):(0.7 -7), (0.8-

[0083] 6.5):(0.8-6.5):(0.8-6.5), (0.9-6):(0.9-6.5):(0.9-6), (0.95-5.5):(0.95-5.5):(0.95-5.5), and (1- 5):(l-5):(l-5).

[0084] In an embodiment of the present invention, the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.75-5):(0.1-2):(0. 1-2.5), (l-4.8):(0.2-

[0085] 1.8):(0.25-2.3), (1.2-4.6):(0.4-1.6):(0.5-2.1), (1.4-4.4):(0.5-1.4):(0.6-1.9), (1.6-4.2):(0.6-

[0086] 1.2):(0.7-1.7), or (2-4):(0.7-l . l):(0.8-1.5).

[0087] In an embodiment of the present invention, the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (l-5):(0.4-2):(l-5), (1.2-4.8):(0.5-

[0088] 1.8):(1.2-4.8), (1.3-4.6):(0.6-1.6):(1.3-4.6), (1.4-4.4):(0.7-1.4):(l .4-4.4), (1.5-4.2):(0.8-

[0089] 1.2):(1.5-4.2), (1.6-4.2):(0.8-1.2):(l .6-4.2), (1.7-4. l):(0.8-1.2):(1.7-4.1), (1 ,8-4):(0.8-1. 1):(1.8- 4), or (2-4):(0.8-l. l):(2-4).

[0090] In an embodiment of the present invention, the amount of (A) epoxidized oil ranges is at least 45 wt%, at least 47.5 wt%, at least 50 wt%, at least 52.5 wt%, at least 55 wt%, at least 57.5 wt%, at least 60 wt%, at least 62.5 wt%, or at least 65 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. The HMPSA composition contains a total of at most 85 wt%, at most 82.5 wt%, at most 80 wt%, at most 77.5 wt%, at most 75 wt%, at most 72.5 wt%, at most 70 wt%, at most 67.5 wt%, or at most 65 wt% of (A) epoxidized oil based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 45 wt% to 85 wt%, 50 wt% to 85 wt%, 55 wt% to 85 wt%, 60 wt% to 85 wt%, 65 wt% to 85 wt%, 45 wt% to 80 wt%, 50 wt% to 80 wt%, 55 wt% to 80 wt%, 60 wt% to 80 wt%, 65 wt% to 80 wt%, 45 wt% to 75 wt%, 50 wt% to 75 wt%, 55 wt% to 75 wt%, 60 wt% to 75 wt%, 65 wt% to 75 wt%, 45 wt% to 70 wt%, 50 wt% to 70 wt%, 55 wt% to 70 wt%, 60 wt% to 70 wt%, and 65 wt% to 70 wt%. In an embodiment of the present invention, the foregoing content of epoxidized oil includes the content of the corresponding non-epoxidized oil that may be present in the Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0091] HMPSA composition.

[0092] In an embodiment of the present invention, the amount of (B) nucleophilic compound is at least 5 wt%, at least 7.5 wt%, at least 10 wt%, at least 12.5 wt%, at least 15 wt%, at least 17.5 wt%, at least 20 wt%, at least 22.5 wt%, or at least 25 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. The HMPSA composition contains a total of at most 35 wt%, at most 32.5 wt%, at most 30 wt%, at most 27.5 wt%, at most 25 wt%, at most 22.5 wt%, at most 20 wt%, at most 17.5 wt%, or at most 15 wt% of (B) nucleophilic compound based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 5 wt% to 35 wt%, 7.5 wt% to 35 wt%, 10 wt% to 35 wt%, 12.5 wt% to 35 wt%, 15 wt% to 35 wt%, 5 wt% to 30 wt%, 7.5 wt% to 30 wt%, 10 wt% to 30 wt%, 12.5 wt% to 30 wt%, 15 wt% to 30 wt%, 5 wt% to 25 wt%, 7.5 wt% to 25 wt%, 10 wt% to 25 wt%, 12.5 wt% to 25 wt%, 15 wt% to 25 wt%, 5 wt% to 20 wt%, 7.5 wt% to 20 wt%, 10 wt% to 20 wt%, 12.5 wt% to 20 wt%, 15 wt% to 20 wt%, 5 wt% to 17.5 wt%, 7.5 wt% to 17.5 wt%, 10 wt% to 17.5 wt%, 12.5 wt% to

[0093] 17.5 wt%, 15 wt% to 17.5 wt%, 5 wt% to 15 wt%, 7.5 wt% to 15 wt%, 10 wt% to 15 wt%, and

[0094] 12.5 wt% to 15 wt%.

[0095] In an embodiment of the present invention, the amount of (C) phenolic compound is at least 7.5 wt%, at least 10 wt%, at least 12.5 wt%, at least 15 wt%, at least 17.5 wt%, at least 20 wt%, at least 22.5 wt%, at least 25 wt%, at least 27.5 wt%, or at least 30 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. The HMPSA composition contains a total of at most 45 wt%, at most 42.5 wt%, at most 40 wt%, at most 37.5 wt%, at most 35 wt%, at most 32.5 wt%, at most 30 wt%, at most

[0096] 27.5 wt%, at most 25 wt%, at most 22.5 wt%, or at most 20 wt% of (C) phenolic compound based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the HMPSA composition. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 7.5 wt% to 40 wt%, 10 wt% to 40 wt%, 12.5 wt% to 40 wt%, 15 wt% to 40 wt%, 20 wt% to 40 wt%, 7.5 wt% to 35 wt%, 10 wt% to 35 wt%,

[0097] 12.5 wt% to 35 wt%, 15 wt% to 35 wt%, 20 wt% to 35 wt%, 7.5 wt% to 30 wt%, 10 wt% to 30 wt%, 12.5 wt% to 30 wt%, 15 wt% to 30 wt%, 20 wt% to 30 wt%, 7.5 wt% to 25 wt%, 10 wt% to 25 wt%, 12.5 wt% to 25 wt%, 15 wt% to 25 wt%, 20 wt% to 25 wt%, 7.5 wt% to 20 Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) wt%, 10 wt% to 20 wt%, 12.5 wt% to 20 wt%, and 15 wt% to 20 wt%.

[0098] In an embodiment of the present invention, the HMPSA composition of the present invention is biobased and / or has low or is free from volatile organic compounds (“VOC”). In an embodiment of the present invention, the HMPSA composition may be composed of one or more bio-based material totaling from 24 wt% to 100 wt% and / or may have high solids of over 60%.

[0099] In an embodiment of the present invention, the HMPSA composition contains a total of at least 24%, at least 25 wt%, at least 27.5 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97.5 wt%, or 100 wt% of bio-based materials (e.g., a plant-based and / or bio-renewable polymer). The HMPSA composition contains a total of at most 100 wt%, at most 97.5 wt%, at most 95wt%, at most 90 wt%, at most 85 wt%, at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 65 wt%, at most 60 wt%, at most 55 wt%, at most 50 wt%, at most 45 wt%, at most 40 wt%, or at most 35 wt% of bio-based materials (e.g., a plant-based and / or biorenewable materials). In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. In the foregoing, the recited wt% is based on the total mass of the HMPSA composition. Exemplary ranges include: 24 wt% to 100 wt%, 30 wt% to 100 wt%, 35 wt% to 100 wt%, 40 wt% to 100 wt%, 45 wt% to 100 wt%, 50 wt% to 100 wt%, 55 wt% to 100 wt%, 60 wt% to 100 wt%, 65 wt% to 100 wt%, 70 wt% to 100 wt%, 75 wt% to 100 wt%, 80 wt% to 100 wt%, 85 wt% to 100 wt%, 90 wt% to 100 wt%, 95 wt% to 100 wt%, 24 wt% to 95 wt%, 30 wt% to 95 wt%, 35 wt% to 95 wt%, 40 wt% to 95 wt%, 45 wt% to 95 wt%, 50 wt% to 95 wt%, 55 wt% to 95 wt%, 60 wt% to 95 wt%, 65 wt% to 95 wt%, 70 wt% to 95 wt%, 75 wt% to 95 wt%, 80 wt% to 95 wt%, 85 wt% to 95 wt%, 90 wt% to 95 wt%, 24 wt% to 90 wt%, 30 wt% to 90 wt%, 35 wt% to 90 wt%, 40 wt% to 90 wt%, 45 wt% to 90 wt%, 50 wt% to 90 wt%, 55 wt% to 90 wt%, 60 wt% to 90 wt%, 65 wt% to 90 wt%, 70 wt% to 90 wt%, 75 wt% to 90 wt%, 80 wt% to 90 wt%, 85 wt% to 90 wt%, 24 wt% to 85 wt%, 30 wt% to 85 wt%, 35 wt% to 85 wt%, 40 wt% to 85 wt%, 45 wt% to 85 wt%, 50 wt% to 85 wt%, 55 wt% to 85 wt%, 60 wt% to 85 wt%, 65 wt% to 85 wt%, 70 wt% to 85 wt%, 75 wt% to 85 wt%, 80 wt% to 85 wt%, 24 wt% to 75 wt%, 30 wt% to 75 wt%, 35 wt% to 75 wt%, 40 wt% to 75 wt%, 45 wt% to 75 wt%, 50 wt% to 75 wt%, 55 wt% to 75 wt%, 60 wt% to 75 wt%, 65 wt% to 75 wt%, 70 wt% to 75 wt%, 24 wt% to 65 wt%, 30 wt% to 65 wt%, 35 wt% to 65 wt%, 40 wt% to 65 wt%, 45 wt% to 65 wt%, 50 wt% Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) to 65 wt%, 55 wt% to 65 wt%, 60 wt% to 65 wt%, 24 wt% to 50 wt%, 30 wt% to 50 wt%, 35 wt% to 50 wt%, and 40 wt% to 50 wt%.

[0100] In an embodiment, after mixing, the HMPSA composition has a high solids content of over 25%, over 30%, over 35%, over 40%, over 45%, over 50%, over 55%, over 60%, over 70%, over 75%, over 80%, over 85%, over 90%, over 95%, over 97.5%, over 98%, or of 100%. Exemplary ranges include from 50 to 100%, from 60 to 100%, from 65 to 100%, from 70 to 100%, from 75 to 100%, from 80 to 100%, from 85 to 100%, from 90 to 100%, from 95 to 100%, from 97.5 to 100%, from 50 to 98%, from 60 to 98%, from 65 to 98%, from 70 to 98%, from 75 to 98%, from 80 to 98%, from 85 to 98%, from 90 to 98%, from 95 to 98%, from 25 to 95%, from 30 to 95%, from 35 to 95%, from 40 to 95%, from 45 to 95%, from 50 to 95%, from 55 to 95%, from 60 to 95%, from 65 to 95%, from 70 to 95%, from 75 to 95%, from 80 to 95%, from 85 to 95%, from 90 to 95%, from 30 to 90%, from 40 to 90%, from 50 to 90%, from 60 to 90%, from 70 to 90%, from 35 to 80%, from 40 to 70%, from 45 to 65%. This very high solids content reduces transportation costs.

[0101] In an embodiment, the HMPSA composition has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is no more than 2 wt%, no more than 1.5 wt%, no more than 1.0 wt%, no more than 0.05 wt%, no more than 0.01 wt% total VOCs. In an embodiment of the invention, the HMPSA is free from VOCs.

[0102] Additives

[0103] The HMPSA composition of the present invention may contain one or more optional additive component s). Exemplary additive components include one or more of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and / or a crosslinker.

[0104] Where the HMPSA composition contains one or more additives, the additives may be added at any step in the preparation of the HMPSA prior to the step of evaporation of the solvents. The additives can be added with or pre-mixed with any of the primary components.

[0105] Where the additive is a solvent, the solvent may be, but is not limited to, alcohols such Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) as ethanol or methanol, water, chloroform, di chloromethane, dimethyl sulfoxide, and dimethyl formamide. The solvent is generally added in an amount and type to assist in the dissolution of the phenolic compound and / or to further tune or optimize the adhesive properties of the HMPSA. Where the additive is a solvent, the solvent has low VOC content or is free from (i.e., has zero) VOCs.

[0106] Where the additive is a nanotube or a microcarrier, the nanotube and / or microcarrier may contain additives including at least one of titanium dioxide, a pigment, and an antimicrobial agent.

[0107] Exemplary catalysts include catalysts include tertiary amines, Mannich bases formed from secondary amines, nitrogen-containing bases, alkali metal hydroxides, alkali phenolates, alkali metal alcoholates, hexahydrothiazines, and organometallic compounds. An exemplary catalyst is dibutyltin dilaurate, an organotin compound. The catalyst may be added, in amount from 0.001 wt % to 10 wt %, based on the total weight of the system. The catalyst may accelerate the curing time of isocyanate moieties (e.g., in the isocyanate component or in prepolymers) and active hydrogens (e.g., polyols and / or chain extenders) to offer mechanical properties.

[0108] The inclusion of a plasticizer may help control the viscosity of the adhesive and improve flexibility.

[0109] The inclusion of a stabilizer may help enhance the shelf life and / or the heat resistance of the HMPSA.

[0110] An exemplary antimicrobial agent is a 2: 1 blend of emulsified water-based silver solution and zinc-pyrithione.

[0111] Dyes and / or pigments (such as titanium dioxide and / or carbon black), may be included in the additive component to impart color properties to the HMPSA composition. Pigments may be in the form of solids or a dispersion in a resin carrier.

[0112] Reinforcements (e.g., flake or milled glass and / or fumed silica), may be used to impart certain properties.

[0113] The HMPSA composition system may be a curable composition that includes curing agent / hardener component in addition to the HMPSA composition or as part of the HMPSA composition. The amount of the hardener component used may vary depending on whether the Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) hardener component is used in addition to or as part of the HMPSA composition. In exemplary embodiments, an amine-based hardener (e.g., one that is known in the art for use in curing epoxy systems) may be excluded because the sprayable polyurethane systems rely on urethane curing chemistry due to minimal residual epoxy content.

[0114] As an adhesion promoter, a hydrogenated rosin (or combinations of two or more different hydrogenated rosins) can be mentioned. Rosin may be synthetically or naturally sourced. In an embodiment, it is preferred to use a naturally sourced rosin. An exemplary source is conifer (e.g., pine) trees.

[0115] In an embodiment of the present invention, the rosin may be selected from gum rosin, wood rosin, tall oil rosin, distilled rosins, dimerized rosins and polymerized rosins. Rosin may be produced by heating fresh liquid resin, which causes the volatile terpene components to evaporate (gum rosin) or be a by-product derived from wood pulping in a kraft process (tailoil rosin).

[0116] The rosin may contain, as a main component, resin acids such as abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, dehydroabietic acid, and sandaracopimaric acid.

[0117] The rosin of the present invention may be partially or fully hydrogenated. Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. Hydrogenation of rosin, more specifically, is a chemical process that alters rosin by adding hydrogen molecules to its double bonds. Such methods are commonly understood by the skilled artisan including conditions for controlling whether the final product is a partially or fully hydrogenate rosin. The final product of full hydrogenation of rosin is the formation of tetrahydroabietic acid.

[0118] In an embodiment of the present invention, the rosin when present may be a gum rosin or a fully hydrogenated gum rosin.

[0119] Other additives include, e.g., UV light stabilizers, antioxidants, air release agents, and adhesion promoters, which may be independently used depending on the desired characteristics of the HMPSA composition.

[0120] The additives addition amount will vary depending upon the end use. In an Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) embodiment, the total amount of all additives (based on the total of the HMPSA composition) is no more than 25 wt% no more than 20 wt%, no more than 15 wt%, not more than 10 wt%, or no more than 5 wt%. As an example, where the additive is a defoamer, the total amount is 2 to 9 wt%, 3 to 8 wt%, or 4 to 7 wt%. Alternatively, where the coting composition contains a UV light stabilizer, the amount ranges from 1 to 4 wt% or 2 to 3 wt%.

[0121] Other exemplary additives and amounts include:

[0122] A reactive surfactant, for example 3-n-pentadecylphenol, with an equivalent weight of from 250 to 300, at an amount of from 1 to 5 wt% or 2 to 4 wt%.

[0123] A diamine with an equivalent weight ranging from 130 to 160, and an amount of from 3 to 9 wt% or 5 to 7 wt%.

[0124] An antimicrobial agent, for example, silver solution and zinc pyrithione, at an amount of from 0.5 to 1.5 wt% or 0.75% to 1.25%.

[0125] A comprehensive review of additives, which may be adapted for HMPSA, is given in “Lehrbuch der Lacke und Beschichtungen [Textbook on paints and coatings], volume III, “Lbsemittel, Weichmacher, Additive, Zwischenprodukte” [Solvents, plasticizers, additives, intermediates], H. Kittel, Verlag W. A. Colomb in der Heenemann GmbH, Berlin- Ob er Schwandorf, 1976, pp. 237-398.

[0126] Method of preparing hot-melt pressure sensitive adhesive composition

[0127] In an embodiment of the present invention is a method of preparing a HMPSA composition. The method entails:

[0128] (a) Mixing (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound,

[0129] (b) Thermally reacting the mixture in (a) for a time and under conditions sufficient to form a HMPSA composition, and

[0130] (c) Cooling the HMPSA composition.

[0131] In the foregoing method, the phenolic compound may be pre-blended with a solvent to tune and / or optimize the adhesion properties of the HMPSA composition. The use of a solvent Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) may also help in the dissolution and incorporation of the phenolic compound. In a particular embodiment, the phenolic compound is tannic acid and the solvent is water.

[0132] Where the phenolic compound is pre-blended with a solvent, the time and conditions of the thermal reaction in (b) is such that the solvent is substantially evaporated (i.e., at least 95%, at least 97.5%, at least 99%, or 100% of the solvent is removed).

[0133] In step (a), (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound can be added in any order.

[0134] In an embodiment, each of (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound is added to a reaction vessel and mixed by stirring.

[0135] In an embodiment, step (a) entails:

[0136] (a’) heating the epoxidized oil,

[0137] (a”) adding the phenolic compound or a pre-blend of a phenolic compound and a solvent to the heated epoxidized oil and mixing, and

[0138] (a’”) adding the nucleophilic compound and mixing.

[0139] In an embodiment, in step (a) the epoxidized oil is heated to decrease the viscosity. Heating in this step may be to a temperature of at least 100 °C, at least 102.5 °C, at least 105 °C, at least 107.5 °C, at least 110 °C, at least 112.5 °C, at least 115 °C, at least 117.5 °C, or at least 120 °C. In step (a), the epoxidized oil may be heated to a temperature of at most 135 °C, at most 132.5 °C, at most 130 °C, at most 127.5 °C, at most 125 °C, at most 122.5 °C, at most 120 °C, at most 117.5 °C, or at most 115 °C. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 100 °C to 135 °C, 105 °C to 135 °C, 110 °C to 135

[0140] °C, 115 °C to 135 °C, 120 °C to 135 °C, 100 °C to 130 °C, 105 °C to 130 °C, 110 °C to 130

[0141] °C, 115 °C to 130 °C, 120 °C to 130 °C, 100 °C to 125 °C, 105 °C to 125 °C, 110 °C to 125

[0142] °C, 115 °C to 125 °C, 120 °C to 125 °C, 100 °C to 120 °C, 105 °C to 120 °C, 110 °C to 120

[0143] °C, and 115 °C to 120 °C.

[0144] In an embodiment, once the epoxidized oil is heated in step (a) as described above, the phenolic compound (or pre-blend of the phenolic compound and solvent) is added to the epoxidized oil and the epoxidized oil and phenolic compound are mixed with stirring. In a variant of this embodiment, the stirring is for a time sufficient to achieve substantial Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) homogeneity. In a variant of this embodiment, the stirring is for a time ranging from 1 to 10 minutes, from 2 to 8 minutes, from 3 to 7 minutes, or from 4 to 6 minutes. In a variant of this embodiment, the temperature is maintained in the foregoing heating temperature range upon the addition of the phenolic compound.

[0145] In an embodiment, after the epoxidized oil and phenolic compound (or pre-blend of the phenolic compound and solvent) are mixed, the nucleophilic compound is added and the components are mixed. In a variant of this embodiment, the temperature is maintained in the foregoing heating temperature range upon the addition of the nucleophilic compound.

[0146] In an embodiment, one or more additives are added in step (a). The additives may be added to or with one or more of (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound.

[0147] In step (b), the mixture is heated to a molten state. In step (b), the mixture is heated to a temperature of at least 100 °C, at least 102.5 °C, at least 105 °C, at least 107.5 °C, at least 110 °C, at least 112.5 °C, at least 115 °C, at least 117.5 °C, or at least 120 °C. In step (b), the mixture is heated to a temperature of at most 135 °C, at most 132.5 °C, at most 130 °C, at most 127.5 °C, at most 125 °C, at most 122.5 °C, at most 120 °C, at most 117.5 °C, or at most 115 °C. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 100 °C to 135 °C, 105 °C to 135 °C, 110 °C to 135 °C, 115 °C to 135 °C, 120 °C to 135 °C,

[0148] 100 °C to 130 °C, 105 °C to 130 °C, 110 °C to 130 °C, 115 °C to 130 °C, 120 °C to 130 °C,

[0149] 100 °C to 125 °C, 105 °C to 125 °C, 110 °C to 125 °C, 115 °C to 125 °C, 120 °C to 125 °C,

[0150] 100 °C to 120 °C, 105 °C to 120 °C, 110 °C to 120 °C, and 115 °C to 120 °C.

[0151] In an embodiment, the temperature in step (b) is greater than the temperature in step (a).

[0152] In an embodiment, the temperature in step (b) is the same as the temperature in step (a).

[0153] In an embodiment, between steps (b) and (c) the mixture is processed into the desired form. The mixture may be poured onto cooling drums, cast onto film, or extruded into sheets, ribbons, or rolls, depending on the end application.

[0154] In step (c), the composition is cooled to ambient temperature. In this embodiment, ambient temperatures include ranges of about 17 °C - 27 °C, 18 °C - 26 °C, 19 °C - 25 °C, and Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0155] 20 °C - 24 °C. In a variant of this embodiment, the HMPSA composition is cooled at a rapid rate. As a rate of cooling, a rate of at least 2.5 °C / min, at least 5 °C / min, at least 7.5 °C / min, at least 10°C / min, at least 12.5 °C / min, or at least 15 °C / min, are mentioned. In step (c), the HMPSA solidifies and becomes less tacky as it cools.

[0156] In an embodiment, the HMPSA can be applied to a substrate before step (c) while the HMPSA composition is still in a molten state.

[0157] In an embodiment, the HMPSA can be applied to a substrate during step (c) while the HMPSA composition is cooling.

[0158] In an embodiment, the HMPSA can be applied to a substrate after step (c) while the HMPSA composition. In this embodiment, it may be necessary to reactivate the HMPSA composition before application to the substrate by application of heat. In this embodiment, the heating temperature for reactivation is any temperature that is sufficient to increase the tackiness and adhesion properties of the HMPSA composition to a level adapted to the specific desired use. Exemplary temperatures include (including ranges bound by any lower limit indicated by “at least” to any upper limit indicated by “at most”) at least 40 °C, at least 45 °C, at least 50 °C, at least 55 °C, at least 60 °C, at least 65 °C, at least 70 °C, at least 75 °C, or at least 80 °C to at most 100 °C, at most 95 °C, at most 90 °C, at most 85 °C, at most 80 °C, at most 75 °C, or at most 70 °C.

[0159] The final HMPSA composition can be collected and packaged according to the needs of the user, which may involve supplying it in rolls, sheets, or in bulk quantities.

[0160] In an embodiment is a HMPSA reaction product obtained by the method described above.

[0161] Pressure sensitive adhesive sheet and method of making pressure sensitive adhesive sheet

[0162] In an embodiment of the present invention, the PSA sheet may by a single-sided PSA sheet or double-sided PSA sheet. Thus, in an embodiment of the present invention, the PSA sheet may contain a substrate (as defined below, the “substrate” within the present invention may be a single or multi-layered substrate) with one or both sides thereof having a PSA layer. Wherein the PSA sheet has both sides having a PSA layer, one or both sides may be a HMPSA of the present invention, while when the PSA sheet is a single-sided PSA the PSA layer is a Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0163] HMPSA layer of the present invention. In an embodiment, the PSA sheet is a double-sided PSA sheet wherein both sides of a substrate have a HMPSA layer of the present invention, wherein the HMPSA layers may be the same or different compositions.

[0164] The PSA sheet may be in the form of a film, a sheet, a ribbon, or a roll.

[0165] The substrate for use in the present invention may be of any form. Examples include sheet-like forms including a resin film, a paper, a cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof. The substrate supports the PSA layer. The substrate may be singlelayered or multi-layered with same species or different species of substrates. Wherein the substrate is single-layered, a layer is meant to refer not only to where there is a single layer, but also to a collection of layers made of the same composition. For example, the singlelayered form includes a form wherein a plurality of layers of the same composition are laminated. Wherein the substrate is multi-layered, a least one layer therein has a composition different from the other layers. Thus, where the substrate is multi-layered all the layers may be different or one or more layers may have the same composition. An illustrative, non-limiting exemplary multi-layered form would be a three-layer substrate where the outer layers have the same composition and the middle layer has a different composition.

[0166] In an embodiment, a substrate having a resin sheet as a main component (resin film substrate) may be used. Examples of the resin constituting the substrate include polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymerized polypropylene, block copolymerized polypropylene, homopolyprolene, polybutene, polymethyl pentene, ethylene- vinyl acetate copolymer (EVA), ionomer, ethylene (meth)acrylic acid ester (random, alternating) copolymer, ethyl ene-butene copolymer, and ethyl ene-hexane copolymer; polyurethane; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); polycarbonates; polyimides; polyether ether ketones; polyether imides; polyamides such as aramid, total aromatic polyamide, and the like; polyphenyl sulfide; fluororesins; polyvinyl chloride; polyvinylidene chloride; cellulose resins; and silicone resins. A single species or a combination of two or more species of resins may be used for formation of the overall or a part of the substrate (for example, any one layer in a substrate having a laminated structure of two or more layers).

[0167] The substrate may have various additives such as fillers (inorganic fillers, organic Atorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) fillers, etc.), antiaging agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.) added thereto according to the requirement.

[0168] The substrate can be manufactured by any well-known and appropriate method. For instance, the substrate can be manufactured by a known method such as a calendar method, a casting method, an inflation extrusion method, or a T-die extrusion method. Moreover, the substrate may be manufactured by performing a stretching treatment.

[0169] The HMPSA layer (and the alternate PSA layer) may be adhered to the substrate through any known method. Examples include a physical treatment such as a corona discharge treatment, a plasma treatment, a sand mat processing treatment, an ozone exposure treatment, a flame exposure treatment, a high-voltage shock treatment, or an ionized radiation treatment; a chemical treatment such as an acid treatment, an alkali treatment, or a chromic acid treatment; an adhesion treatment entailing a coating agent (undercoating agent).

[0170] In an embodiment, a conductive vapor-deposited layer containing a metal, an alloy, or an oxide thereof may be provided on the surface of the substrate for the purpose of imparting antistatic ability.

[0171] In an embodiment, an undercoat layer is provided on the surface of the substrate on the side of the HMPSA layer and / or PSA layer. In this embodiment, an undercoat layer may be disposed between the substrate and the HMPSA layer and / or PSA layer. A material forming the undercoat layer is not particularly limited. Examples of materials for use in an undercoat layer include one species or two or more species of resins including a urethane (polyisocyanate) resin, a polyester resin, an acrylic resin, a polyamide resin, a melamine resin, an olefin resin, a polystyrene resin, an epoxy resin, a phenol resin, an isocyanurate resin, and a polyvinyl acetate resin.

[0172] The undercoat layer may be formed by using a known or commonly used coater such as a gravure roll coater, or a reverse roll coater. The thickness of the undercoat layer is not particularly limited and may generally be in the range of about 0.1 pm to 10 pm, 0.1 to 7.5 pm, 0.1 to 5 pm, 0.1 to 4 pm, 0.1 to 3 pm, 0.1 to 2.5 pm, 0.1 to 2 pm, 0.1 to 1 pm, 0.25 pm to 10 pm, 0.25 to 7.5 pm, 0.25 to 5 pm, 0.25 to 4 pm, 0.25 to 3 pm, 0.25 to 2.5 pm, 0.25 to 2 pm, 0.25 to 1 pm, 0.5 pm to 10 pm, 0.5 to 7.5 pm, 0.5 to 5 pm, 0.5 to 4 pm, 0.5 to 3 pm, 0.5 to 2.5 pm, 0.5 to 2 pm, 0.5 to 1 pm, 0.75 pm to 10 pm, 0.75 to 7.5 pm, 0.75 to 5 pm, 0.75 to 4 pm, 0.75 to 3 pm, 0.75 to 2.5 pm, 0.75 to 2 pm, 0.75 to 1 pm, 1 pm to 10 pm, 1 to 7.5 pm, 1 to 5 Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) m, 1 to 4 pm, 1 to 3 pm, 1 to 2.5 pm, 1 to 2 pm, 1.5 pm to 10 pm, 1.5 to 7.5 pm, 1.5 to 5 pm,

[0173] 1.5 to 4 pm, 1.5 to 3 pm, 1.5 to 2.5 pm, 1.5 to 2 pm, 2 pm to 10 pm, 2 to 7.5 pm, 2 to 5 pm, 2 to 4 pm, 2 to 3 pm, 2 to 2.5 pm, 2.5 pm to 10 pm, 2.5 to 7.5 pm, 2.5 to 5 pm, 2.5 to 4 pm, or

[0174] 2.5 to 3 pm.

[0175] In an embodiment, the PSA sheet has a rear-surface treatment layer, especially when the PSA sheet is a single-sided PSA. The rear-surface treatment agent for forming a rearsurface treatment layer is not particularly limited. Examples include, a silicone-based rearsurface treatment agent, a fluorine-based rear-surface treatment agent, a long-chain alkyl-based rear-surface treatment agent, and other known and commonly used treatment agents can be used according to the purpose and application. In an embodiment, wherein the PSA sheet is stored as a roll form, the rear-surface treatment layer may serve as a protective release liner.

[0176] In an embodiment, the PSA sheet of the present invention may contain a removable release liner affixed on the outward exposed surface of the pressure-sensitive adhesive layer (either the HMPSA layer and / or the PSA layer).

[0177] Thus, when the pressure-sensitive adhesive layer (either the HMPSA layer and / or the PSA layer) is exposed, the pressure-sensitive adhesive layer may be protected with the release- treated sheet (also referred to as a separator or protective release liner) before practical use. The release-treated sheet is then peeled off before actual use.

[0178] In an embodiment, a silicone release liner is used as the release-treated sheet. Examples of a material for forming the separator include a plastic film such as a polyethylene, polypropylene, polyethylene terephthalate, or polyester film, a porous material such as paper, cloth and nonwoven fabric, and an appropriate thin material such as a net, a foamed sheet, a metal foil, and a laminate thereof. In particular, a plastic film is preferably used, because of its good surface smoothness.

[0179] The plastic film may be any film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

[0180] If necessary, the separator (protective release liner) may be treated with a release agent such as a silicone, fluorine, long-chain alkyl, or fatty acid amide release agent, or may be Atorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) subjected to release and antifouling treatment with silica powder or to antistatic treatment of coating type, kneading and mixing type, vapor-deposition type, or the like. In particular, if the surface of the separator is appropriately subjected to release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment, the releasability from the pressure-sensitive adhesive layer can be further increased.

[0181] The thickness of the separator (i.e., release-treated sheet) is generally from about 5 to about 200 pm, from about 5 to about 175 pm, from about 5 to about 150 pm, from about 5 to about 125 pm, from about 5 to about 100 pm, from about 5 to about 75 pm, from about 5 to about 50 pm, from about 5 to about 25 pm, from about 25 to about 200 pm, from about 25 to about 175 pm, from about 25 to about 150 pm, from about 25 to about 125 pm, from about 25 to about 100 pm, from about 25 to about 75 pm, from about 25 to about 50 pm, from about 50 to about 200 pm, from about 50 to about 175 pm, from about 50 to about 150 pm, from about 50 to about 125 pm, from about 50 to about 100 pm, from about 50 to about 75 pm, from about 100 to about 200 pm, from about 100 to about 175 pm, from about 100 to about 150 pm, or from about 100 to about 125 pm.

[0182] The thickness of the substrate is not particularly limited, and it can be appropriately selected according to the purpose, but generally, the thickness may be about 2 pm to 800 pm. From the viewpoint of processability and handleability of the PSA sheet, it is appropriate that the thickness of the substrate is at least 2 pm, at least 5 pm, at least 10 pm, at least 20 pm, at least 30 pm, at least 40 pm, at least 50 pm, at least 60 pm, at least 70 pm, at least 80 pm, at least 100 pm, at least 125 pm, or at least 150 pm. Moreover, from the viewpoint of flexibility, it is appropriate that the upper-limit of the thickness of the substrate is at most 800 pm, at most 750 pm, at most 700 pm, at most 650 pm, at most 600 pm, at most 550 pm, at most 500 pm, at most 450 pm, at most 400 pm, at most 350 pm, at most 300 pm, at most 250 pm, at most 200 pm, at most 175 pm, at most 150 pm, at most 125 pm, at most 100 pm, at most 80 pm, at most 75 pm, at most 70 pm, at most 65 pm, or at most 60 pm. In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include: 2 pm to 800 pm, 5 pm to 800 pm, 10 pm to 800 pm, 20 pm to 800 pm, 50 pm to 800 pm, 75 pm to 800 pm, 100 pm to 800 pm, 125 pm to 800 pm, 150 pm to 800 pm, 2 pm to 600 pm, 5 pm to 600 pm, 10 pm to 600 pm, 20 pm to 600 pm, 50 pm to 600 pm, 75 pm to 600 pm, 100 pm to 600 pm, 125 pm to 600 pm, 150 pm to 600 pm, 2 pm to 500 pm, 5 pm to 500 pm, 10 pm to 500 pm, 20 pm to 500 pm, 50 pm to 500 pm, 75 pm to 500 pm, 100 pm to 500 pm, 125 pm to 500 pm, 150 pm to 500 pm, 2 pm Attorney Docket No. 40787 / 65 (BIOB- 18 / 01W0) to 400 pm, 5 pm to 400 pm, 10 pm to 400 pm, 20 pm to 400 pm, 50 pm to 400 pm, 75 pm to 400 pm, 100 pm to 400 pm, 125 pm to 400 pm, 150 pm to 400 pm, 2 pm to 300 pm, 5 pm to 300 pm, 10 pm to 300 pm, 20 pm to 300 pm, 50 pm to 300 pm, 75 pm to 300 pm, 100 pm to 300 pm, 125 pm to 300 pm, 150 pm to 300 pm, 2 pm to 250 pm, 5 pm to 250 pm, 10 pm to 250 pm, 20 pm to 250 pm, 50 pm to 250 pm, 75 pm to 250 pm, 100 pm to 250 pm, 125 pm to 250 pm, or 150 pm to 250 pm.

[0183] The total thickness of the PSA sheet (may include the PSA layer and the substrate, but does not include the release liner) disclosed herein is not particularly limited, and it is appropriately in the range of about 10 pm to 1200 pm, 15 pm to 1200 pm, 20 pm to 1200 pm, 25 pm to 1200 pm, 30 pm to 1200 pm, 40 pm to 1200 pm, 50 pm to 1200 pm, 60 pm to 1200 pm, 70 pm to 1200 pm, 80 pm to 1200 pm, 90 pm to 1200 pm, 100 pm to 1200 pm, 10 pm to 1000 pm, 15 pm to 1200 pm, 20 pm to 1000 pm, 25 pm to 1000 pm, 30 pm to 1000 pm, 40 pm to 1000 pm, 50 pm to 1000 pm, 60 pm to 1000 pm, 70 pm to 1000 pm, 80 pm to 1000 pm, 90 pm to 1000 pm, 100 pm to 1000 pm, 10 pm to 800 pm, 15 pm to 800 pm, 20 pm to 800 pm, 25 pm to 800 pm, 30 pm to 800 pm, 40 pm to 800 pm, 50 pm to 800 pm, 60 pm to 800 pm, 70 pm to 800 pm, 80 pm to 800 pm, 90 pm to 800 pm, 100 pm to 800 pm, 10 pm to 600 pm, 15 pm to 600 pm, 20 pm to 600 pm, 25 pm to 600 pm, 30 pm to 600 pm, 40 pm to 600 pm, 50 pm to 600 pm, 60 pm to 600 pm, 70 pm to 600 pm, 80 pm to 600 pm, 90 pm to 600 pm, 100 pm to 600 pm, 10 pm to 400 pm, 15 pm to 400 pm, 20 pm to 400 pm, 25 pm to 400 pm, 30 pm to 400 pm, 40 pm to 400 pm, 50 pm to 400 pm, 60 pm to 400 pm, 70 pm to 400 pm, 80 pm to 400 pm, 90 pm to 400 pm, 100 pm to 400 pm, 10 pm to 300 pm, 15 pm to 300 pm, 20 pm to 300 pm, 25 pm to 300 pm, 30 pm to 300 pm, 40 pm to 300 pm, 50 pm to 300 pm, 60 pm to 300 pm, 70 pm to 300 pm, 80 pm to 300 pm, 90 pm to 300 pm, 100 pm to 300 pm, 10 pm to 200 pm, 15 pm to 200 pm, 20 pm to 200 pm, 25 pm to 200 pm, 30 pm to 200 pm, 40 pm to 200 pm, 50 pm to 200 pm, 60 pm to 200 pm, 70 pm to 200 pm, 80 pm to 200 pm, 90 pm to 200 pm, or 100 pm to 200 pm.

[0184] In an embodiment, the HMPSA is solvent-free. As used herein, “solvent-free” means not including a solvent practically. In this context, the HMPSA is “solvent-free” when the solvent content of the HMPSA is at most 1 wt%, at most 0.75 wt%, at most 0.5 wt%, at most 0.25 wt%, at most 0.1 wt%, at most 0.075 wt%, at most 0.05 wt%, at most 0.025 wt%, at most 0.01 wt%, or 0 wt%. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0185] Method of using hot-melt pressure sensitive adhesive sheet

[0186] In an embodiment of the present invention is a method of adhering a surface of a first material to a surface of second material, which may be the same or different, by:

[0187] (a) Applying a HMPSA composition according to the present invention to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic),

[0188] (b) Heating the HMPSA composition to a temperature sufficient to reactivate (i.e., increase the tackiness and adhesion properties) the HMPSA composition,

[0189] (c) Contacting the surface of the first material to the surface of the second surface, and

[0190] (d) Allowing the HMPSA composition to cool to ambient temperature.

[0191] In the foregoing embodiment, when applied to a substrate the HMPSA becomes tacky upon heating, allowing it to bond to various surfaces without the need for external solvents or curing processes. The adhesive can be reactivated with heat, making it suitable for pressuresensitive applications such as labels, tapes, and medical devices.

[0192] In the foregoing methods, application thickness will vary based upon the materials to be adhered, the adherence strength desired, the HMPSA composition viscosity and solids content when prepared, and the form of the HMPSA composition. In an embodiment, the HMPSA composition is in the form of a film or tape. In general, the application thickness (of the individual components or the mixed adhesive composition) ranges from 0.001 to 0.500 inches (1 - 500 mils), from 0.002 to 0.250 inches (2 - 250 mils), from 0.003 to 0.200 inches (3 - 200 mils), from 0.004 to 0.100 inches (4 to 100 mils), or from 0.005 to 0.050 inches (5 to 50 mils). Of course, thinner applications are also envisioned of from 1 to 50 mils, 2 to 25 mils, 3 to 20 mils, 4 to 15 mils, or 5 to 10 mils.

[0193] In this embodiment, the heating temperature for reactivation is any temperature that is sufficient to increase the tackiness and adhesion properties of the HMPSA composition to a level adapted to the specific desired use. Exemplary temperatures include (including ranges Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) bound by any lower limit indicated by “at least” to any upper limit indicated by “at most”) at least 40 °C, at least 45 °C, at least 50 °C, at least 55 °C, at least 60 °C, at least 65 °C, at least 70 °C, at least 75 °C, or at least 80 °C to at most 100 °C, at most 95 °C, at most 90 °C, at most 85 °C, at most 80 °C, at most 75 °C, or at most 70 °C.

[0194] In this embodiment, “ambient temperature” ambient temperatures include ranges of about 17 °C - 27 °C, 18 °C - 26 °C, 19 °C - 25 °C, and 20 °C - 24 °C.

[0195] In an embodiment of the present invention is a method of adhering a surface of a first material to a surface of second material, which may be the same or different, by:

[0196] (a) Removing a release-treated sheet or release liner from a pressure-sensitive (PSA) sheet comprising a hot-melt pressure sensitive adhesive (HMPSA) as described herein to expose the HMPSA composition

[0197] (b) Applying the PSA sheet to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic), and

[0198] (c) Contacting the surface of the first material to the surface of the second surface.

[0199] The foregoing method can be utilized with a single-sided PSA sheet (commonly used in, e.g., a label, tape, packaging, including boxes or envelopes) or a double-sided PSA sheet (commonly used in any situation where two surfaces are intended to be bonded to each other).

[0200] In an embodiment, the surface to be coated has a moisture content of no more than 25%, no more than 20%, no more than 15%, no more than 10%, or no more than 5% as measured with an electronic moisture meter.

[0201] Prior to application of the PSA sheet to a surface(s), the surface(s) may pretreated and / or cleaned.

[0202] In an embodiment, the PSA sheet can be applied when the first substrate and / or the second substrate are exposed to dry, moist, wet, or underwater conditions.

[0203] In an embodiment, the surface(s) to be adhered may be cleaned prior to application of Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) the PSA sheet. For example, to facilitate proper adherence, the surface can be cleaned to remove dirt, debris, grime, minerals such as lime and calcium, oils, release agents, grease, mud, excess mortar, and mold and mildew, etc.

[0204] In an embodiment, the surface may be pretreated with a primer (e.g., smooth surfaces) or a sealer or filler to remove pinholes (e.g., porous surfaces). Another envisioned pretreatment includes pointing and / or caulking all cracks. Further, all voids, beeholes, masonry surface defects and openings such as conduits, pipes, drains, door frames, vents, air conditioner openings, electrical openings, control joints, or any dissimilar materials should be repaired using urethane or other approved patching.

[0205] Another form of surface pretreatment envisioned in the present invention includes fluting, scoring, sandblasting, and / or etching as well as raking joints.

[0206] In an embodiment, the PSA sheet is not applied where freezing temperatures have existed prior to application. In such a situation, adequate time should be allowed for the application surface to thaw. In an embodiment, air, surface, and material temperatures should be above 40°F (4.4°C) and at least 5°F above the dew point prior to application. Further, it is not desirable to apply the PSA sheet where temperatures are below 40°F or when temperatures are expected to drop below 40°F within 48 hours of application. For exterior surfaces, application should also be avoided if rain, snow, or lower temperatures are expected within 48 hours. Further, the PSA sheet would be adversely affective if relative humidity is greater than 90% and, therefore, it should be avoided.

[0207] Substrates

[0208] The HMPSA composition of the present invention finds utility in many different industries including packaging, woodworking, commercial & personal mobile transportation (including automotive), construction, home repair, home renovation, household, flooring, carpeting, tiling, oil and gas, steel fabrication, bridge and highway, power generation, pharmaceutical, aerospace, marine, drones, electronics, clothing, apparel, shoes, crafts, food processing, veterinary, hospitals, and restaurants. Of particular note, use of the HMPSA of the present invention may be particularly advantageous for use in labels, tapes, packaging, medical devices, construction adhesives, and commercial & personal mobile transportation (including automotive) assembly. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0209] The HMPSA composition is suitable for and has excellent adherence properties with a broad scope of materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic (including polyvinyl chloride (PVC) or polytetrafluoroethylene (Teflon)). Further, the HMPSA composition is suitable for and has excellent adherence properties when two different materials are used.

[0210] Benefits of HMPSA

[0211] In some embodiments, the HMPSA composition of the present invention provides one or more of the following advantages over PSAs:

[0212] • Bio-based and Sustainable: The primary components are derived from renewable resources, reducing reliance on petroleum-based materials.

[0213] • High Solids Content: The 100% solids composition eliminates the need for solvents, reducing VOC emissions and environmental impact.

[0214] • Excellent Adhesion: The tannic acid pre-blend provides strong adhesion to a variety of substrates.

[0215] • Tunable Properties: The composition and process parameters can be adjusted to achieve desired adhesive properties.

[0216] The present invention is exemplified by the following embodiments:

[0217] [1] A hot-melt pressure sensitive adhesive composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound dissolved in a solvent.

[0218] [2] The hot-melt pressure sensitive adhesive composition of [1], wherein the epoxidized oil is derived from a natural oil.

[0219] [3] The hot-melt pressure sensitive adhesive composition of [1] or [2], wherein the natural oil is selected from the group consisting of a plant oil, a vegetable oil, a tree oil, a nut oil, or an animal oil.

[0220] [4] The hot-melt pressure sensitive adhesive composition of any one of [1] - [3], Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) wherein the natural oil has one or more non-conjugated carbon-carbon double bonds.

[0221] [5] The hot-melt pressure sensitive adhesive composition of any one of [1] - [4], wherein the natural oil is directly epoxidized.

[0222] [6] The hot-melt pressure sensitive adhesive composition of any one of [1] - [5], wherein prior to epoxidation, the natural oil is subjected to a dehydrogenation reaction to introduce one or more non-conjugated carbon-carbon double bonds into one more carboxylic chain of a constituent saturated fatty acid.

[0223] [7] The hot-melt pressure sensitive adhesive composition of any one of [1] - [6], wherein the natural oil of the epoxidized oil is at least one oil selected from the group consisting of almond oil, avocado oil, bay oil, basil oil, bergamot oil, oils derived from biomass, Brazil nut oil, broccoli oil, cade oil, canola oil, caraway seed oil, cashew oil, cashew nutshell liquid, cinnamon leaf oil, citronella java oil, citrus seed oil, cod liver oil, corn oil, cocoa butter, cottonseed oil, cumin oil, cypress oil, fish oil, flaxseed oil, geranium oil, grapefruit oil, hazelnut oil, lavender oil, lemongrass oil, linseed oil, macademia nut oil, mandarine oil, melissa oil, myrtle oil, neem oil, nutmeg oil, oat oil, olive oil, palm oil, palmarosa oil, peanut oil, pecan oil, peppermint oil, pine nut oil, pistachio oil, rapeseed oil, safflower oil, sage oil, sesame oil, soybean oil, spearmint oil, sunflower oil, high oleic sunflower oil, tea tree oil, thyme oil, triolein, vegetable oil, Vernonia oil, vetiver Haiti oil, walnut oil, wormwood oil, ylang ylang oil.

[0224] [8] The hot-melt pressure sensitive adhesive composition of any one of [1] - [7], wherein the epoxidized oil has a degree of epoxidation of 100%.

[0225] [9] The hot-melt pressure sensitive adhesive composition of any one of [1] - [8], wherein the epoxidized oil has a degree of epoxidation of at least 10%.

[0226]

[0010] The hot-melt pressure sensitive adhesive composition of any one of [1] - [9], wherein the epoxidized oil is epoxidized soybean oil.

[0227]

[0011] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0010] , wherein the epoxidized oil has a viscosity of 100 to 1000 cps at 25°C.

[0228]

[0012] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0011] , wherein the nucleophilic compound contains at least two reactive functional groups.

[0229]

[0013] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0012] , Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) wherein the nucleophilic compound is at least one compound selected from the group consisting of malic acid, glycerol, adipic acid, azelic acid, dodecanoic acid, maleic acid, itoconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, fumaric acid and succinic acid.

[0230]

[0014] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0013] , wherein the nucleophilic compound is glycerol.

[0231]

[0015] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0014] , wherein the nucleophilic compound is malic acid.

[0232]

[0016] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0015] , wherein the phenolic compound is at least one compound selected from the group consisting of phenol, cresol, guaiacol, apiole, carnosol, carvacrol, xylenol, dillapiole, eugenol, rosemarinol, capsaicin, methyl salicylate, butylated hydroxytoluene, 4-nonylphenol, tyrosine, thymol, raspberry ketone, orthophenyl phenol, gallol, pyrogallol, bisphenol A, juglone, estradiol, sesamol, serotonin, 3,4-dihydroxybenzadehyde, quercetin, fingerol, kaempferol, myricetin, rutin, isorhamnetin, fesperidin, naringenin, silybin, eriodictyol, apigenin, tangeritin, luteolin, catechins, (+)-catechin, (+)-gallocatechin, (-)-epicate chin, (-)-epigallocatechin, (-)- epigallocatechin gallate (EGCG), (-)-epicatechin 3 -gallate, theaflavin, theaflavin-3 -gallate, theaflavin-3 '-gallate, theaflavin-3, 3 '-digallate, thearubigins, pelargonidin, peonidin, cyanidin, delphinidin, malvidin, petunidin, phytoestrogens, daidzein, genistein, glycitein, dihydroflavonols, chaicones, coumestrol, ellagic acid, gallic acid, tannic acid, 3,4- dihydroxybenzoic acid, picric acid, salicylic acid, vanillin, curcumin, caffeic acid, chlorogenic acid, cinnamic acid, ferulic acid, coumarin, silymarin, secoisolariciresinol, pinoresinol lariciresinol, tyrosol, hydroxytyrosol, oleocanthal, oleuropein, resveratrol, pterostilbene, piceatannol, and lignin.

[0233]

[0017] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0016] , wherein the phenolic compound is at least one compound selected from the group consisting of catechol, vanillin, gallic acid, caffeic acid, juglone, gallol, lignin, tannic acid, 3,4- dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, quercitin, and (+) catechin hydrate.

[0234]

[0018] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0017] , wherein the phenolic compound is catechol.

[0235]

[0019] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0018] , Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) wherein the phenolic compound is gallic acid.

[0236]

[0020] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0019] , wherein the phenolic compound is tannic acid.

[0237]

[0021] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0020] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0. l-10):(0. l-10):(0.1-10).

[0238]

[0022] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0021] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.75-5):(0.1-2):(0.1-2.5).

[0239]

[0023] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0022] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (1 -5):(0.4-2):(l -5).

[0240]

[0024] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0023] , wherein the amount of (A) epoxidized oil ranges from 25 to 85 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0241]

[0025] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0024] , wherein the amount of (B) nucleophilic compound ranges from 5 to 35 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0242]

[0026] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0025] , wherein the amount of (C) phenolic compound ranges from 7.5 to 45 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0243]

[0027] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0026] , wherein the adhesive composition contains a total content of bio-based material ranging from 24 wt% to 100 wt%.

[0244]

[0028] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0027] , wherein the adhesive composition contains a solids content ranging from 60 to 100%. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0245]

[0029] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0028] , wherein the adhesive composition contains a total volatile organic compounds content of no more than 2 wt%.

[0246]

[0030] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0029] , wherein the adhesive composition is free from volatile organic compounds.

[0247]

[0031] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0030] , further comprising one or more additives and said additives are selected from the group consisting of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and a crosslinker.

[0248]

[0032] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0031] , wherein the phenolic compound is dissolved in a solvent and is at a concentration of 0.001 g / mL to 2 g / ml.

[0249]

[0033] The hot-melt pressure sensitive adhesive composition of any one of [1] -

[0032] , wherein the solvent is water.

[0250]

[0034] A method of making a hot-melt pressure sensitive adhesive composition comprising:

[0251] (a) Mixing (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound,

[0252] (b) Thermally reacting the mixture in (a) for a time and under conditions sufficient to form a HMPSA composition, and

[0253] (c) Cooling the HMPSA composition.

[0254]

[0035] The method of claim

[0034] , wherein the phenolic compound is pre-blended with a solvent.

[0255]

[0036] The method of

[0034] or

[0035] , wherein the solvent is water.

[0256]

[0037] The method of any one of

[0034] -

[0036] , wherein the concentration of the phenolic Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) compound after pre-blending with solvent is 0.001 g / mL to 2 g / ml.

[0257]

[0038] The method of any one of

[0034] -

[0037] , wherein the solvent is substantially evaporated in step (c).

[0258]

[0039] The method of any one of

[0034] -

[0038] , wherein in step (a) comprises:

[0259] (a’) heating the epoxidized oil to 100 °C to 135 °C,

[0260] (a”) adding the phenolic compound or a pre-blend of a phenolic compound and a solvent to the heated epoxidized oil and mixing, and

[0261] (a’”) adding the nucleophilic compound and mixing.

[0262]

[0040] The method of

[0039] , wherein in (a”) the temperature is maintained in the range of 100 °C to 135 °C during said mixing.

[0263]

[0041] The method of any one of

[0039] -

[0040] , wherein in (a’”) the temperature is maintained in the range of 100 °C to 135 °C during said mixing.

[0264]

[0042] The method of any one of

[0034] -

[0041] , wherein one or more additives are added in step (a). The additives may be added to or with one or more of (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound.

[0265]

[0043] The method of any one of

[0034] -

[0042] , wherein said one or more additives are selected from the group consisting of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and a crosslinker.

[0266]

[0044] The method of any one of

[0034] -

[0043] , wherein said thermally reacting is at a temperature of 100 °C to 135 °C.

[0267]

[0045] The method of any one of

[0034] -

[0044] , wherein between steps (b) and (c) the mixture is processed into the desired form.

[0268]

[0046] The method of any one of

[0034] -

[0045] , wherein processing entails pouring onto cooling drums, casting onto a film, or extruding into sheets, ribbons, or rolls. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0269]

[0047] The method of any one of

[0034] -

[0046] , wherein between steps (b) and (c) the mixture is applied to a substrate.

[0270]

[0048] The method of any one of

[0034] -

[0047] , wherein in step (c) the HMPSA composition is cooled to ambient temperature.

[0271]

[0049] The method of any one of

[0034] -

[0048] , wherein during step (c) the HMPSA composition is applied to a substrate.

[0272]

[0050] The method of any one of

[0034] -

[0049] , wherein after step (c) the HMPSA composition is applied to a substrate.

[0273]

[0051] The method of any one of

[0034] -

[0050] , wherein the HMPSA composition is reactivated prior to application by heating the HMPSA composition to a temperature of 40 °C to 100 °C.

[0274]

[0052] The method of any one of

[0034] -

[0051] , wherein the epoxidized oil is derived from a natural oil.

[0275]

[0053] The method of any one of

[0034] -

[0052] , wherein the natural oil is selected from the group consisting of a plant oil, a vegetable oil, a tree oil, a nut oil, or an animal oil.

[0276]

[0054] The method of any one of

[0034] -

[0053] , wherein the natural oil has one or more nonconjugated carbon-carbon double bonds.

[0277]

[0055] The method of any one of

[0034] -

[0054] , wherein the natural oil is directly epoxidized.

[0278]

[0056] The method of any one of

[0034] -

[0055] , wherein prior to epoxidation, the natural oil is subjected to a dehydrogenation reaction to introduce one or more non-conjugated carboncarbon double bonds into one more carboxylic chain of a constituent saturated fatty acid.

[0279]

[0057] The method of any one of

[0034] -

[0056] , wherein the natural oil of the epoxidized oil is at least one oil selected from the group consisting of almond oil, avocado oil, bay oil, basil oil, bergamot oil, oils derived from biomass, Brazil nut oil, broccoli oil, cade oil, canola oil, caraway seed oil, cashew oil, cashew nutshell liquid, cinnamon leaf oil, citronella java oil, citrus seed oil, cod liver oil, corn oil, cocoa butter, cottonseed oil, cumin oil, cypress oil, fish oil, flaxseed oil, geranium oil, grapefruit oil, hazelnut oil, lavender oil, lemongrass oil, linseed oil, macademia nut oil, mandarine oil, melissa oil, myrtle oil, neem oil, nutmeg oil, oat oil, olive oil, palm oil, palmarosa oil, peanut oil, pecan oil, peppermint oil, pine nut oil, pistachio Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) oil, rapeseed oil, safflower oil, sage oil, sesame oil, soybean oil, spearmint oil, sunflower oil, high oleic sunflower oil, tea tree oil, thyme oil, triolein, vegetable oil, Vernonia oil, vetiver Haiti oil, walnut oil, wormwood oil, ylang ylang oil.

[0280]

[0058] The method of any one of

[0034] -

[0057] , wherein the epoxidized oil has a degree of epoxidation of 100%.

[0281]

[0059] The method of any one of

[0034] -

[0058] , wherein the epoxidized oil has a degree of epoxidation of at least 10%.

[0282]

[0060] The method of any one of

[0034] -

[0059] , wherein the epoxidized oil is epoxidized soybean oil.

[0283]

[0061] The method of any one of

[0034] -

[0060] , wherein the epoxidized oil has a viscosity of 100 to 1000 cps at 25°C.

[0284]

[0062] The method of any one of

[0034] -

[0061] , wherein the nucleophilic compound contains at least two reactive functional groups.

[0285]

[0063] The method of any one of

[0034] -

[0062] , wherein the nucleophilic compound is at least one compound selected from the group consisting of malic acid, glycerol, adipic acid, azelic acid, dodecanoic acid, maleic acid, itoconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, fumaric acid and succinic acid.

[0286]

[0064] The method of any one of

[0034] -

[0063] , wherein the nucleophilic compound is glycerol.

[0287]

[0065] The method of any one of

[0034] -

[0064] , wherein the nucleophilic compound is malic acid.

[0288]

[0066] The method of any one of

[0034] -

[0065] , wherein the phenolic compound is at least one compound selected from the group consisting of phenol, cresol, guaiacol, apiole, camosol, carvacrol, xylenol, dillapiole, eugenol, rosemarinol, capsaicin, methyl salicylate, butylated hydroxytoluene, 4-nonylphenol, tyrosine, thymol, raspberry ketone, orthophenyl phenol, gallol, pyrogallol, bisphenol A, juglone, estradiol, sesamol, serotonin, 3,4- dihydroxybenzadehyde, quercetin, fingerol, kaempferol, myricetin, rutin, isorhamnetin, fesperidin, naringenin, silybin, eriodictyol, apigenin, tangeritin, luteolin, catechins, (+)- catechin, (+)-gallocatechin, (-)-epicate chin, (-)-epigallocatechin, (-)-epigallocatechin gallate (EGCG), (-)-epicatechin 3 -gallate, theaflavin, theaflavin-3 -gallate, theaflavin-3 '-gallate, Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) theaflavin-3, 3 '-digallate, thearubigins, pelargonidin, peonidin, cyanidin, delphinidin, malvidin, petunidin, phytoestrogens, daidzein, genistein, glycitein, dihydroflavonols, chaicones, coumestrol, ellagic acid, gallic acid, tannic acid, 3,4-dihydroxybenzoic acid, picric acid, salicylic acid, vanillin, curcumin, caffeic acid, chlorogenic acid, cinnamic acid, ferulic acid, coumarin, silymarin, secoisolariciresinol, pinoresinol lariciresinol, tyrosol, hydroxytyrosol, oleocanthal, oleuropein, resveratrol, pterostilbene, piceatannol, and lignin.

[0289]

[0067] The method of any one of

[0034] -

[0066] , wherein the phenolic compound is at least one compound selected from the group consisting of catechol, vanillin, gallic acid, caffeic acid, juglone, gallol, lignin, tannic acid, 3,4-dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, quercitin, and (+) catechin hydrate.

[0290]

[0068] The method of any one of

[0034] -

[0067] , wherein the phenolic compound is catechol.

[0291]

[0069] The method of any one of

[0034] -

[0068] , wherein the phenolic compound is gallic acid.

[0292]

[0070] The method of any one of

[0034] -

[0069] , wherein the phenolic compound is tannic acid.

[0293]

[0071] The method of any one of

[0034] -

[0070] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0. l-10):(0. l-10):(0.1-10).

[0294]

[0072] The method of any one of

[0034] -

[0071] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.75-5):(0.1-2):(0.1-2.5).

[0295]

[0073] The method of any one of

[0034] -

[0072] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (1 -5):(0.4-2):(l -5).

[0296]

[0074] The method of any one of

[0034] -

[0073] , wherein the amount of (A) epoxidized oil ranges from 25 to 85 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0297]

[0075] The method of any one of

[0034] -

[0074] , wherein the amount of (B) nucleophilic compound ranges from 5 to 35 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0298]

[0076] The method of any one of

[0034] -

[0075] , wherein the amount of (C) phenolic compound ranges from 7.5 to 45 wt% based on the total mass of (A) epoxidized oil, (B) Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0299]

[0077] The method of any one of

[0034] -

[0076] , wherein the adhesive composition contains a total content of bio-based material ranging from 24 wt% to 100 wt%.

[0300]

[0078] The method of any one of

[0034] -

[0077] , wherein the adhesive composition contains a solids content ranging from 60 to 100%.

[0301]

[0079] The method of any one of

[0034] -

[0078] , wherein the adhesive composition contains a total volatile organic compounds content of no more than 2 wt%.

[0302]

[0080] The method of any one of

[0034] -

[0079] , wherein the adhesive composition is free from volatile organic compounds.

[0303]

[0081] A hot-melt pressure sensitive adhesive composition produced by the method of any one of

[0034] -

[0080] ,

[0304]

[0082] A pressure-sensitive adhesive sheet with at least one hot-melt pressure sensitive adhesive layer comprising a hot-melt pressure sensitive adhesive composition on a substrate, wherein the hot-melt pressure sensitive adhesive composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound.

[0305]

[0083] The pressure-sensitive adhesive sheet of

[0082] , wherein the pressure-sensitive adhesive sheet in the form of a film, a sheet, a ribbon, or a roll.

[0306]

[0084] The pressure-sensitive adhesive sheet of

[0082] or

[0083] , wherein the substrate is a resin film, a paper, a cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof.

[0307]

[0085] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0084] , wherein the surface of the hot-melt pressure sensitive adhesive that is opposite the substrate is covered by a protective release liner.

[0308]

[0086] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0085] , wherein the protective release liner is treated with a release agent or is subjected to release and antifouling treatment.

[0309]

[0087] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0086] , wherein the epoxidized oil is derived from a natural oil.

[0310]

[0088] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0087] , wherein the natural Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) oil is selected from the group consisting of a plant oil, a vegetable oil, a tree oil, a nut oil, or an animal oil.

[0311]

[0089] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0088] , wherein the natural oil has one or more non-conjugated carbon-carbon double bonds.

[0312]

[0090] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0089] , wherein the natural oil is directly epoxidized.

[0313]

[0091] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0090] , wherein prior to epoxidation, the natural oil is subjected to a dehydrogenation reaction to introduce one or more non-conjugated carbon-carbon double bonds into one more carboxylic chain of a constituent saturated fatty acid.

[0314]

[0092] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0091] , wherein the natural oil of the epoxidized oil is at least one oil selected from the group consisting of almond oil, avocado oil, bay oil, basil oil, bergamot oil, oils derived from biomass, Brazil nut oil, broccoli oil, cade oil, canola oil, caraway seed oil, cashew oil, cashew nutshell liquid, cinnamon leaf oil, citronella java oil, citrus seed oil, cod liver oil, corn oil, cocoa butter, cottonseed oil, cumin oil, cypress oil, fish oil, flaxseed oil, geranium oil, grapefruit oil, hazelnut oil, lavender oil, lemongrass oil, linseed oil, macademia nut oil, mandarine oil, melissa oil, myrtle oil, neem oil, nutmeg oil, oat oil, olive oil, palm oil, palmarosa oil, peanut oil, pecan oil, peppermint oil, pine nut oil, pistachio oil, rapeseed oil, safflower oil, sage oil, sesame oil, soybean oil, spearmint oil, sunflower oil, high oleic sunflower oil, tea tree oil, thyme oil, triolein, vegetable oil, Vernonia oil, vetiver Haiti oil, walnut oil, wormwood oil, ylang ylang oil.

[0315]

[0093] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0092] , wherein the epoxidized oil has a degree of epoxidation of 100%.

[0316]

[0094] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0093] , wherein the epoxidized oil has a degree of epoxidation of at least 10%.

[0317]

[0095] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0094] , wherein the epoxidized oil is epoxidized soybean oil.

[0318]

[0096] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0095] , wherein the epoxidized oil has a viscosity of 100 to 1000 cps at 25°C.

[0319]

[0097] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0096] , wherein the Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) nucleophilic compound contains at least two reactive functional groups.

[0320]

[0098] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0097] , wherein the nucleophilic compound is at least one compound selected from the group consisting of malic acid, glycerol, adipic acid, azelic acid, dodecanoic acid, maleic acid, itoconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, fumaric acid and succinic acid.

[0321]

[0099] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0098] , wherein the nucleophilic compound is glycerol.

[0322]

[0100] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0099] , wherein the nucleophilic compound is malic acid.

[0323]

[0101] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0100] , wherein the phenolic compound is at least one compound selected from the group consisting of phenol, cresol, guaiacol, apiole, carnosol, carvacrol, xylenol, dillapiole, eugenol, rosemarinol, capsaicin, methyl salicylate, butylated hydroxytoluene, 4-nonylphenol, tyrosine, thymol, raspberry ketone, orthophenyl phenol, gallol, pyrogallol, bisphenol A, juglone, estradiol, sesamol, serotonin, 3,4-dihydroxybenzadehyde, quercetin, fingerol, kaempferol, myricetin, rutin, isorhamnetin, fesperidin, naringenin, silybin, eriodictyol, apigenin, tangeritin, luteolin, catechins, (+)-catechin, (+)-gallocatechin, (-)-epicate chin, (-)-epigallocatechin, (-)- epigallocatechin gallate (EGCG), (-)-epicatechin 3 -gallate, theaflavin, theaflavin-3 -gallate, theaflavin-3 '-gallate, theaflavin-3, 3 '-digallate, thearubigins, pelargonidin, peonidin, cyanidin, delphinidin, malvidin, petunidin, phytoestrogens, daidzein, genistein, glycitein, dihydroflavonols, chaicones, coumestrol, ellagic acid, gallic acid, tannic acid, 3,4- dihydroxybenzoic acid, picric acid, salicylic acid, vanillin, curcumin, caffeic acid, chlorogenic acid, cinnamic acid, ferulic acid, coumarin, silymarin, secoisolariciresinol, pinoresinol lariciresinol, tyrosol, hydroxytyrosol, oleocanthal, oleuropein, resveratrol, pterostilbene, piceatannol, and lignin.

[0324]

[0102] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0101] , wherein the phenolic compound is at least one compound selected from the group consisting of catechol, vanillin, gallic acid, caffeic acid, juglone, gallol, lignin, tannic acid, 3,4- dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, quercitin, and (+) catechin hydrate.

[0325]

[0103] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0102] , wherein the phenolic compound is catechol. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0326]

[0104] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0103] , wherein the phenolic compound is gallic acid.

[0327]

[0105] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0104] , wherein the phenolic compound is tannic acid.

[0328]

[0106] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0105] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.1-10):(0.1-10):(0.1-10).

[0329]

[0107] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0106] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.75-5):(0.1-2):(0.1-2.5).

[0330]

[0108] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0107] , wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (l-5):(0.4-2):(l-5).

[0331]

[0109] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0108] , wherein the amount of (A) epoxidized oil ranges from 25 to 85 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0332]

[0110] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0109] , wherein the amount of (B) nucleophilic compound ranges from 5 to 35 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0333]

[0111] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0110] , wherein the amount of (C) phenolic compound ranges from 7.5 to 45 wt% based on the total mass of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

[0334]

[0112] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0111] , wherein the adhesive composition contains a total content of bio-based material ranging from 24 wt% to 100 wt%.

[0335]

[0113] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0112] , wherein the adhesive composition contains a solids content ranging from 60 to 100%. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0336]

[0114] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0113] , wherein the adhesive composition contains a total volatile organic compounds content of no more than 2 wt%.

[0337]

[0115] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0114] , wherein the adhesive composition is free from volatile organic compounds.

[0338]

[0116] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0115] , further comprising one or more additives and said additives are selected from the group consisting of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and a crosslinker.

[0339]

[0117] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0116] , wherein the phenolic compound is dissolved in a solvent and is at a concentration of 0.001 g / mL to 2 g / ml.

[0340]

[0118] The pressure-sensitive adhesive sheet of any one of

[0082] -

[0117] , wherein the solvent is water.

[0341]

[0119] A method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:

[0342] (a) Applying a hot-melt pressure sensitive (HMPSA) composition according to any one of [1] -

[0033] or produced by the method of any one of

[0034] -

[0080] to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic,

[0343] (b) Heating the HMPSA composition to a temperature sufficient to reactivate the HMPSA composition,

[0344] (c) Contacting the surface of the first material to the surface of the second surface, and

[0345] (d) Allowing the HMPSA composition to cool to ambient temperature. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0346]

[0120] The method of

[0119] , wherein said heating is at a temperature of 40 °C to 100 °C.

[0347]

[0121] A method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:

[0348] (a) Removing a release-treated sheet or release liner from a pressure-sensitive (PSA) sheet of any one of

[0082] -

[0117] or comprising a hot-melt pressure sensitive adhesive (HMPSA) composition according to any one of [1] -

[0033] or produced by the method of any one of

[0034] -

[0080] to expose the HMPSA composition,

[0349] (b) Applying the PSA sheet to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic, and

[0350] (c) Contacting the surface of the first material to the surface of the second surface.

[0351] In the context of the present description, all publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth, and shall be considered part of the present disclosure in their entirety.

[0352] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

[0353] The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others or ordinary skill in the art to understand the embodiments Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) disclosed herein.

[0354] Except where expressly noted, trademarks are shown in upper case.

[0355] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.

[0356] When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range. Further, where a numerical limit or range is stated herein, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out.

[0357] Further, unless otherwise explicitly stated to the contrary, when one or multiple ranges or lists of items are provided, this is to be understood as explicitly disclosing any single stated value or item in such range or list, and any combination thereof with any other individual value or item in the same or any other list.

[0358] When the term “about” is used, it is used to mean a certain effect or result can be obtained within a certain tolerance, and the skilled person knows how to obtain the tolerance. Exemplary tolerance includes within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range. When the term "about" is used in describing a value or an endpoint of a range, the disclosure should be understood to include the specific value or end-point referred to.

[0359] The term "substantially" can allow for a degree of variability in a value or range, for example, within 90%, within 95%, or within 99% of a stated value or of a stated limit of a range.

[0360] As used herein, the terms “containing,” "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a nonexclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0361] The transitional phrase "consisting of excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0362] The transitional phrase "consisting essentially of limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel character! stic(s) of the claimed invention. A “consisting essentially of’ claim occupies a middle ground between closed claims that are written in a “consisting of’ format and fully open claims that are drafted in a “comprising” format. Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term “consisting essentially of’.

[0363] As used herein, an "embodiment" means that a particular feature, structure or characteristic is included in at least one or more manifestations, examples, or implementations of this invention. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art. Combinations of features of different embodiments are all meant to be within the scope of the invention, without the need for explicitly describing every possible permutation by example. Thus, any of the claimed embodiments can be used in any combination.

[0364] Further, unless expressly stated to the contrary, “and / or” refers to an inclusive and not to an exclusive. Thus, “and / or” should be understood to mean “either or both” of the elements so conjoined, e.g., elements that are conjunctively present in some cases and disjunctively present in other cases. For example, a condition A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0365] The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. Similarly, the adjective “another,” when used to introduce an element, is intended to mean one or more elements. The terms “including” and “having” are intended to be inclusive such that there may be additional elements other than the listed elements. Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)

[0366] The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description.

[0367] As used herein, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials.

[0368] The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description.

[0369] Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made only by way of illustration and that numerous changes in the details of construction and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention.

[0370] The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein.

[0371] Having generally described this invention, a further understanding can be obtained by reference to certain specific examples, which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.

[0372] EXAMPLES

[0373] Example 1 - Synthesis of HMPSA composition

[0374] Epoxidized soybean oil (ESO) is added to a vessel and heated to 115 °C. Allow for the Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) oil to heat up and then add a 1 : 1 (w / v) tannic acid / water pre-blend into the oil. Allow 5 minutes of mixing followed by the addition of a granulated malic acid to the mixture. The ratio of ESO:malic acid:tannic acid is 5: 1 : 1.25. Heat until water evaporates off and subsequent foaming action happens. This indicates 5 minutes until end of reaction. At this point the HMPSA composition can be applied to a substrate, molded, or extruded into a film, a sheet, a ribbon, or a roll.

[0375] Numerous modifications and variations on the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein.

Claims

Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)49What we claim is:

1. A hot-melt pressure sensitive adhesive (HMPSA) composition comprising:(A) an epoxidized oil derived from a natural oil selected from the group consisting of a plant oil, a vegetable oil, a tree oil, a nut oil, and an animal oil,(B) at least one nucleophilic compound selected from the group consisting of malic acid, glycerol, adipic acid, azelic acid, dodecanoic acid, maleic acid, itoconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, fumaric acid and succinic acid, and(C) at least one phenolic compound dissolved in a solvent, wherein said phenolic compound is selected from the group consisting of phenol, cresol, guaiacol, apiole, carnosol, carvacrol, xylenol, dillapiole, eugenol, rosemarinol, capsaicin, methyl salicylate, butylated hydroxytoluene, 4-nonylphenol, tyrosine, thymol, raspberry ketone, orthophenyl phenol, gallol, pyrogallol, bisphenol A, juglone, estradiol, sesamol, serotonin, 3,4- dihydroxybenzadehyde, quercetin, fingerol, kaempferol, myricetin, rutin, isorhamnetin, fesperidin, naringenin, silybin, eriodictyol, apigenin, tangeritin, luteolin, catechins, (+)- catechin, (+)-gallocatechin, (-)-epicate chin, (-)-epigallocatechin, (-)-epigallocatechin gallate (EGCG), (-)-epicatechin 3-gallate, theaflavin, theaflavin-3 -gallate, theaflavin-3 '- gallate, theaflavin-3, 3'-digallate, thearubigins, pelargonidin, peonidin, cyanidin, delphinidin, malvidin, petunidin, phytoestrogens, daidzein, genistein, glycitein, dihydroflavonols, chaicones, coumestrol, ellagic acid, gallic acid, tannic acid, 3,4-dihydroxybenzoic acid, picric acid, salicylic acid, vanillin, curcumin, caffeic acid, chlorogenic acid, cinnamic acid, ferulic acid, coumarin, silymarin, secoisolariciresinol, pinoresinol lariciresinol, tyrosol, hydroxytyrosol, oleocanthal, oleuropein, resveratrol, pterostilbene, piceatannol, and lignin, wherein the mass ratio of (A) epoxidized oil, (B) nucleophilic compound, and (C) phenolic compound is (0.75-5):(0.1-2):(0.1-2.5).

2. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the natural oil of the epoxidized oil is at least one oil selected from the group consisting of almond oil, avocado oil, bay oil, basil oil, bergamot oil, oils derived from biomass, Brazil nutAttorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) oil, broccoli oil, cade oil, canola oil, caraway seed oil, cashew oil, cashew nutshell liquid, cinnamon leaf oil, citronella java oil, citrus seed oil, cod liver oil, corn oil, cocoa butter, cottonseed oil, cumin oil, cypress oil, fish oil, flaxseed oil, geranium oil, grapefruit oil, hazelnut oil, lavender oil, lemongrass oil, linseed oil, macademia nut oil, mandarine oil, melissa oil, myrtle oil, neem oil, nutmeg oil, oat oil, olive oil, palm oil, palmarosa oil, peanut oil, pecan oil, peppermint oil, pine nut oil, pistachio oil, rapeseed oil, safflower oil, sage oil, sesame oil, soybean oil, spearmint oil, sunflower oil, high oleic sunflower oil, tea tree oil, thyme oil, triolein, vegetable oil, Vernonia oil, vetiver Haiti oil, walnut oil, wormwood oil, ylang ylang oil.

3. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the epoxidized oil is a soybean oil.

4. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the nucleophilic compound is glycerol or malic acid.

5. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the phenolic compound is at least one compound selected from the group consisting of catechol, vanillin, gallic acid, caffeic acid, juglone, gallol, lignin, tannic acid, 3,4- dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, quercitin, and (+) catechin hydrate.

6. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the phenolic compound is selected from the group consisting of catechol, gallic acid, and tannic acid.

7. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the amount of (A) epoxidized oil ranges from 25 to 85 wt%, the amount of (B) nucleophilic compound ranges from 5 to 35 wt%, and the amount of (C) phenolic compound ranges from 7.5 to 45 wt%, where the wt% is based on the total mass of (A) epoxidized oil, (B)Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) nucleophilic compound, and (C) phenolic compound in the adhesive composition.

8. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the adhesive composition contains a total content of bio-based material ranging from 24 wt% to 100 wt%.

9. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the adhesive composition contains a solids content ranging from 60 to 100%.

10. The hot-melt pressure sensitive adhesive composition of claim 1, wherein the adhesive composition contains a total volatile organic compounds content of no more than 2 wt%.

11. The hot-melt pressure sensitive adhesive composition of claim 1, further comprising one or more additives and said additives are selected from the group consisting of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and a crosslinker.

12. A method of making the hot-melt pressure sensitive adhesive composition of claim 1, comprising:(a) Mixing (A) the epoxidized oil, (B) the nucleophilic compound, and (C) the phenolic compound,(b) Thermally reacting the mixture in (a) for a time and under conditions sufficient to form a HMPSA composition, wherein said conditions compriseAttorney Docket No. 40787 / 65 (BIOB- 18 / 01WO) a reaction temperature of 100 °C to 135 °C, and(c) Cooling the HMPSA composition.

13. The method of claim 12, wherein the phenolic compound is pre-blended with a solvent prior to said mixing and the solvent is substantially evaporated in step (c).

14. The method of claim 12, wherein in step (a) comprises:(a’) heating the epoxidized oil to 100 °C to 135 °C,(a”) adding the phenolic compound or a pre-blend of a phenolic compound and a solvent to the heated epoxidized oil and mixing, and(a’”) adding the nucleophilic compound and mixing.

15. The method of claim 14, wherein in (a”) and / or in (a’”) the temperature is maintained in the range of 100 °C to 135 °C during said mixing.

16. The method of claim 12, wherein one or more additives are added in step (a), wherein said one or more additives are selected from the group consisting of a solvent, a promoter, a defoamer, a deaerating agent, a wetting agent, a dispersant, a levelling agent, a dispersed paraffin wax, a thickener, a rheology modifier, an emulsifier, a dye, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a tackifier, a filler, a reinforcement, a chain extender, a stabilizer, a filler, UV light stabilizers, antioxidants, air release agents, adhesion promoters, and a crosslinker.

17. The method of claim 12, wherein said method further comprises processing the mixture between steps (b) and (c) into a desired form, wherein said processing comprises pouring onto cooling drums, casting onto a film, or extruding into sheets, ribbons, or rolls.Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)18. The method of claim 12, wherein said method further comprises applying the mixture to a substrate between steps (b) and (c).

19. The method of claim 12, wherein in step (c) the HMPSA composition is cooled to ambient temperature.

20. The method of claim 12, wherein during or after step (c) the HMPSA composition is applied to a substrate.

21. A pressure-sensitive adhesive sheet with at least one hot-melt pressure sensitive adhesive layer comprising a hot-melt pressure sensitive adhesive composition of claim 1 on a substrate, wherein the hot-melt pressure sensitive adhesive composition comprising (A) an epoxidized oil, (B) a nucleophilic compound, and (C) a phenolic compound.

22. The pressure-sensitive adhesive sheet of claim 21, wherein the pressure-sensitive adhesive sheet in the form of a film, a sheet, a ribbon, or a roll.

23. The pressure-sensitive adhesive sheet of claim 21, wherein the substrate is a resin film, a paper, a cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof.

24. The pressure-sensitive adhesive sheet of claim 21, wherein the surface of the hot- melt pressure sensitive adhesive that is opposite the substrate is covered by a protective release liner.

25. The pressure-sensitive adhesive sheet of claim 21, wherein the protective release liner is treated with a release agent or is subjected to release and antifouling treatment.Attorney Docket No. 40787 / 65 (BIOB- 18 / 01WO)26. A method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:(a) Applying a hot-melt pressure sensitive (HMPSA) composition according to claim 1 to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic,(b) Heating the HMPSA composition to a temperature sufficient to reactivate the HMPSA composition, wherein said temperature is in the range of 40 °C to 100 °C,(c) Contacting the surface of the first material to the surface of the second surface, and(d) Allowing the HMPSA composition to cool to ambient temperature.

27. A method of adhering a surface of a first material to a surface of second material, which may be the same or different, comprising:(a) Removing a release-treated sheet or release liner from a pressure-sensitive (PSA) sheet comprising a hot-melt pressure sensitive adhesive (HMPSA) composition according to claim 1 to expose the HMPSA composition,(b) Applying the PSA sheet to a surface of one or both materials, wherein the materials may be the same or different materials and are selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic, and(c) Contacting the surface of the first material to the surface of the second surface.

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