Thickened starch-based adhesive

Abstract

The present invention provides to an adhesive composition that that is cost-effective, renewable, biodegradable, and exhibits superior bonding strength, water resistance, microbial resistance, durability, and versatility. The adhesive is formulated to be easily applied and cured at ambient temperatures, without the need for mixing or specialized equipment. The unique combination of ingredients provides a strong and lasting bond on a variety of substrates, including metals, plastics, wood, and composites. The adhesive composition contains: a bio-based component; a base polymer; a zinc-containing compound; and a solvent that has low or is free from volatile organic compounds. The adhesive may further contain one or more additives.

Description

[0001] Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0002] TITLE OF THE INVENTION

[0003] THICKENED STARCH-BASED ADHESIVE

[0004] CROSS-REFERENCE TO RELATED APPLICATIONS

[0005] The present application claims priority to U.S. Provisional Appl. No. 63 / 735,660, filed December 18, 2024, the entire contents of which are incorporated herein by reference.

[0006] FIELD OF THE INVENTION

[0007] The present invention relates to the field of adhesives, specifically to a starch-based adhesive composition with improved adhesive properties. The adhesive composition contains a base bio-component, a base polymer, a zinc-containing compound, and a solvent. The adhesive composition has low or is free from volatile organic compounds (“VOC”). The adhesive composition may contain bio-based material(s) totaling from 24% to 95%. The adhesive of the present invention has sufficiently high bonding strength, durability, and versatility so as to be useful in many applications including furniture and other wood to wood applications, flooring including ceramic tiles and wood flooring, metal to metal applications including appliances, glass to glass applications including arts and crafts, paper packaging including cardboard, textile to textile applications, and mixed substrate applications.

[0008] DISCUSSION OF THE BACKGROUND

[0009] In contemporary society it is exposure to toxic glues and coatings is unavoidable. 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 petroleum-based building block (such as ethylene oxide and / or propylene oxide). While such Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) 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. 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.

[0010] Starch-based adhesives have gained recent attention due to their low cost, renewability, and biodegradability. However, conventional starch adhesives often suffer from limitations such as low cohesive strength, poor water resistance, and susceptibility to microbial attack. These limitations restrict their use in many applications.

[0011] In view of the foregoing, there remains a critical need in the art to develop safe and effective adhesives.

[0012] SUMMARY OF THE INVENTION

[0013] It is an object of the present invention to provide an adhesive composition that is cost- effective, renewable, biodegradable, and exhibits superior bonding strength, water resistance, microbial resistance, durability, and versatility. The adhesive is formulated to be easily applied and cured at ambient temperatures, without the need for mixing or specialized equipment. The unique combination of ingredients provides a strong and lasting bond on a variety of substrates, including metals, plastics, wood, and composites.

[0014] The adhesive composition contains: a bio-based component; a base polymer; a zinc- containing compound; and a solvent that has low or is free from volatile organic compounds. The adhesive may further contain one or more additives.

[0015] A kit containing the adhesive composition together with instructions for use thereof.

[0016] A method of making an adhesive composition, by Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) stirring, shaking, or agitating a bio-based component, a base polymer, a zinc- containing compound, and a solvent that has low or is free from volatile organic compounds for a time and under conditions sufficient to blend the bio-based component, the base polymer, and the zinc-containing compound in the solvent to substantial homogeneity thus forming the adhesive composition.

[0017] A method of adhering a surface of a first material to a surface of second material by:

[0018] (1) applying a layer of an adhesive composition comprising a bio-based component, a base polymer, a zinc-containing compound, and a solvent that has low or is free from volatile organic compounds, and, optionally, one or more additives to a surface of one or both materials, wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal, galvanized, steel, ungalvanized steel, tile, paper packaging (e.g., cardboard), composites, textile and plastic, and

[0019] (2) contacting the surface of the first material to the surface of the second surface; and

[0020] (3) allowing the adhesive composition to cure.

[0021] A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises a cured product of a bio-based component, a base polymer, a zinc-containing compound, and a solvent that has low or is free from volatile organic compounds and has at least 24 wt% of the bio-based component based on the total solids content of the adhesive.

[0022] The above objects highlight certain aspects of the invention. Additional objects, aspects and embodiments of the invention are found in the following detailed description of the invention.

[0023] DETAILED DESCRIPTION OF THE INVENTION Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0024] 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.

[0025] 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.

[0026] The present invention provides an adhesive composition (also referred to herein, interchangeably as an “adhesive”) containing: a bio-based component; a base polymer; a zinc-containing compound; and a solvent that has low or is free from volatile organic compounds.

[0027] In an embodiment, the bio-based component is a starch. As a starch, corn starch, potato starch, and tapioca starch, or mixtures thereof, are mentioned as examples. In an embodiment, the bio-based component is a mixture of a starch and one or more plant-based and / or bio-renewable polymer. In an embodiment, the bio-based component is com starch. In an embodiment, the bio-based component is a potato starch.

[0028] The adhesive composition contains a total of at least 5 wt%, at least 7.5 wt%, at least 10 wt%, at least 12.5wt%, at least 15 wt%, at least 17.5 wt%, or at least 20 wt% of bio-based component. The adhesive composition contains a total of at most 40 wt%, at most 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, or at most 15 wt% of the bio-based component. In an embodiment of the invention is any range or sub-range bound by a lower Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0029] (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include 5 wt% to 40 wt%, 7.5 wt% to 40 wt%, 10 wt% to 40 wt%, 12.5 wt% to 40 wt%, 15 wt% to 40 wt%, 17.5 wt% to 40 wt%, 20 wt% to 40 wt%, 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%, 17.5 wt% to 35 wt%, 20 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%, 17.5 wt% to 30 wt%, 20 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%, 17.5 wt% to 25 wt%, and 20 wt% to 25 wt%.

[0030] In an embodiment, the base polymer is any polymer that acts as a binder and improves the water resistance of the adhesive. In an embodiment, the base polymer is any polymer or polymer dispersion that imparts to the adhesive adhesion strength, flexibility, and durability. In embodiment, the base polymer is a water-based emulsions or suspensions, where the polymer is dispersed in a liquid medium.

[0031] Polymer dispersions provide adhesive formulations with specific properties suited for different applications, balancing factors such as tackiness, strength, flexibility, and environmental resistance. Further, incorporating water-based polymers offers safer handling and lower environmental impact compared to solvent-based adhesives. Thus, within the scope of the present invention, the polymer may be selected based on the desired use and / or formulation.

[0032] Exemplary' base polymers include: acrylic polymers: polyvinyl acetate (PVA), styrene-butadiene rubber (SBR), ethylene vinyl acetate (EVA), polyurethane dispersions (PUDs), and vinyl acetate ethylene (VAE).

[0033] In an embodiment, the base polymer may be a polyvinyl alcohol (PVA), an ethyl vinyl acetate, or mixtures thereof (e.g., a poly(vinyl alcohol) stabilized vinyl acetate-ethylene (VAE) copolymer). Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0034] In an embodiment, the base polymer is polyvinyl alcohol.

[0035] The adhesive composition contains a total of at least 35 wt%, at least 40 wt%, at least

[0036] 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, or at least 65 wt% of a base polymer. The adhesive 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%, at most 65 wt%, at most 62.5 wt%, at most 60 wt%, at most 57.5 wt%, or at most 55 wt% of a base polymer. 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 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%, 35 wt% to 80 wt%, 40 wt% to 80 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%, 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%, and 65 wt% to 75 wt%.

[0037] In an embodiment, ethylene vinyl acetate derived from sugar cane could be used as a bio-based component. Thus, as an alternative embodiment, the ethylene vinyl acetate derived from sugar cane could replace the ethylene vinyl acetate as a base polymer in part or in totality. For example, where the ethylene vinyl acetate derived from sugar cane replaces all the ethylene vinyl acetate as a base polymer, the amount of base polymer would be 0 wt% and the bio-based component content can be > 90 wt%.

[0038] In an embodiment, the zinc-containing compound is any compound that provides zinc ions including, without intending to limit the scope, zinc oxide, zinc chloride, zinc sulfate, or mixtures thereof.

[0039] The adhesive composition contains a total of at least 0.25 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3 wt%, at least 3.5 wt%, at least 4 wt%, or at least 5 wt% of a zinc-containing compound. The adhesive Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) composition contains a total of at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7.5 wt%, at most 7 wt%, at most 6.5 wt%, at most 6 wt%, at most 5.5 wt%, at most 5 wt%, at most 4.5 wt%, or at most 4 wt% of a zinc-containing compound. 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 0.25 wt% to 10 wt%, 0.5 wt% to 10 wt%, 1 wt% to 10 wt%, 1.5 wt% to 10 wt%, 2 wt% to 10 wt%, 2.5 wt% to 10 wt%, 3 wt% to 10 wt%, 3.5 wt% to 10 wt%, 4 wt% to 10 wt%, 4.5 wt% to 10 wt%, 5 wt% to 10 wt%, 0.25 wt% to 8 wt%, 0.5 wt% to 8 wt%, 1 wt% to 8 wt%, 1.5 wt% to 8 wt%, 2 wt% to 8 wt%, 2.5 wt% to 8 wt%, 3 wt% to 8 wt%, 3.5 wt% to 8 wt%, 4 wt% to 8 wt%, 4.5 wt% to 8 wt%, 5 wt% to 8 wt%, 0.25 wt% to 6 wt%, 0.5 wt% to 6 wt%, 1 wt% to 6 wt%, 1.5 wt% to 6 wt%, 2 wt% to 6 wt%, 2.5 wt% to 6 wt%, 3 wt% to 6 wt%, 3.5 wt% to 6 wt%, 4 wt% to 6 wt%, 4.5 wt% to 6 wt%, and 5 wt% to 6 wt%.

[0040] In an embodiment, examples of the solvent include, but are not limited to, alcohols such as ethanol or methanol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide. In an embodiment, the solvent is water-based (i.e., a solvent is contained in water). In an embodiment, the solvent is water.

[0041] The adhesive composition contains a total of at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 3 wt%, at least 3.5 wt%, at least 4 wt%, 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%, or at least 20 wt% of a solvent. The adhesive composition contains a total of at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 7.5 wt%, or at most 5 wt% of a solvent. 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 1 wt% to 25 wt%, 1.5 wt% to 25 wt%, 2 wt% to 25 wt%, 2.5 wt% to 25 wt%, 3 wt% to 25 wt%, 3.5 wt% to 25 wt%, 4 wt% to 25 wt%, 5 wt% to 25 wt%, 7.5 wt% to 25 wt%, 10 Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) wt% to 25 wt%, 1 wt% to 15 wt%, 1.5 wt% to 15 wt%, 2 wt% to 15 wt%, 2.5 wt% to 15 wt%, 3 wt% to 15 wt%, 3.5 wt% to 15 wt%, 4 wt% to 15 wt%, 5 wt% to 15 wt%, 7.5 wt% to 15 wt%, 10 wt% to 15 wt%, 1 wt% to 7.5 wt%, 1.5 wt% to 7.5 wt%, 2 wt% to 7.5 wt%, 2.5 wt% to 7.5 wt%, 3 wt% to 7.5 wt%, 3.5 wt% to 7.5 wt%, 4 wt% to 7.5 wt%, 5 wt% to 7.5 wt%, 1 wt% to 5 wt%, 1.5 wt% to 5 wt%, 2 wt% to 5 wt%, 2.5 wt% to 5 wt%, 3 wt% to 5 wt%, 3.5 wt% to 5 wt%, or 4 wt% to 5 wt%.

[0042] In an embodiment, the solvent has a low VOC content.

[0043] In an embodiment, the solvent is free of VOCs.

[0044] In an embodiment, the composition is free from organic solvents.

[0045] In an embodiment, the adhesive composition has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.05 wt%, less than 0.01 wt% total VOCs.

[0046] In an embodiment, the adhesive composition has no odor.

[0047] In an embodiment, the adhesive composition has a pH after mixing ranging from 4.0 to 8.0, from 4.5 to 8.0, from 5.0 to 8.0, from 5.5 to 8.0, from 6.0 to 8.0, from 6.5 to 7.5, from 6.7 to 7.3, from 6.9 to 7.1.

[0048] In an embodiment, the adhesive composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps. As a lower viscosity limit, at least 1,000 cps, at least 1,500 cps, at least 2,000 cps, at least 2,500 cps, at least 3,000 cps, at least 3,500 cps, at least 4,000 cps, at least 4,500 cps, at least 5,000 cps, at least 7,500 cps, at least 10,000 cps, at least 12,500 cps at least 15,000 cps, at least 17,500 cps, and at least 20,000 cps are mentioned. As an upper viscosity limit, at most 30,000 cps, at most 27,500 cps, at most 25,000 cps, at most 22,500 cps, at most 20,000 cps, at most 17,500 cps, at most 15,000 cps, at most 12,500 cps, at most

[0049] 10,000 cps, at most 7,500 cps, at most 5,000 cps, at most 3,500 cps, at most 3,000 cps, at most 2,500 cps, at and at most 2,000 cps are mentioned. Ranges and sub-ranges based on a Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) selection of a lower limit and an upper limit from the foregoing are mentioned. Exemplary viscosity ranges include formulations having a viscosity of 1,000 to 30,000 cps, 2,500 to

[0050] 30,000 cps, 5,000 to 30,000 cps, 7,500 to 30,000 cps, 10,000 to 30,000 cps, 12,500 to 30,000 cps, 15,000 to 30,000 cps, 17,500 to 30,000 cps, 20,000 to 30,000 cps, 1,000 to 25,000 cps,

[0051] 2,500 to 25,000 cps, 5,000 to 25,000 cps, 7,500 to 25,000 cps, 10,000 to 25,000 cps, 12,500 to 25,000 cps, 15,000 to 25,000 cps, 17,500 to 25,000 cps, 20,000 to 25,000 cps, 1,000 to 20,000 cps, 2,500 to 20,000 cps, 5,000 to 20,000 cps, 7,500 to 20,000 cps, 10,000 to 20,000 cps, 12,500 to 20,000 cps, 15,000 to 20,000 cps, 17,500 to 20,000 cps, 1,000 to 15,000 cps,

[0052] 2,500 to 15,000 cps, 5,000 to 15,000 cps, 7,500 to 15,000 cps, 10,000 to 15,000 cps, 12,500 to 15,000 cps, 1,000 to 10,000 cps, 1,500 to 10,000 cps, 2,000 to 10,000 cps, 2,500 to 10,000 cps, 3,000 to 10,000 cps, 3,500 to 10,000 cps, 4,000 to 10,000 cps, 4,500 to 10,000 cps, 5,000 to 10,000 cps, 7,500 to 10,000 cps, 1,000 to 7,500 cps, 1,500 to 7,500 cps, 2,000 to 7,500 cps,

[0053] 2,500 to 7,500 cps, 3,000 to 7,500 cps, 3,500 to 7,500 cps, 4,000 to 7,500 cps, 4,500 to 7,500 cps, 5,000 to 7,500 cps, 1,000 to 5,000 cps, 1,500 to 5,000 cps, 2,000 to 5,000 cps, 2,500 to 5,000 cps, 3,000 to 5,000 cps, 3,500 to 5,000 cps, and 4,000 to 5,000 cps.

[0054] The adhesive 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%, or at least 60 wt% of bio-based materials (e.g., the bio-based component as well as other plant-based and / or bio-renewable polymers). The adhesive composition contains a total of 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., the biobased component as well as other plant-based and / or bio-renewable polymers). 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: 24 wt% Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) to 95 wt%, 30 wt% to 95 wt%, 35 wt% to 95 wt%, 40 wt% to 95 wt%, 24 wt% to 85 wt%, 30 wt% to 85 wt%, 35 wt% to 85 wt%, 40 wt% to 85 wt%, 24 wt% to 75 wt%, 30 wt% to 75 wt%, 35 wt% to 75 wt%, 40 wt% to 75 wt%, 24 wt% to 65 wt%, 30 wt% to 65 wt%, 35 wt% to 65 wt%, 40 wt% to 65 wt%, 24 wt% to 50 wt%, 30 wt% to 50 wt%, 35 wt% to 50 wt%, 40 wt% to 50 wt%, 24 wt% to 40 wt%, 30 wt% to 40 wt%, 35 wt% to 40 wt%, 24 wt% to 35 wt%, 25 wt% to 35 wt%, and 27.5 wt% to 35 wt%.

[0055] In an embodiment, after mixing, the adhesive 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 98%, or over 99% for example from 50 to 98%, from 55 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 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 35 to 80%, from 40 to 70%, from 45 to 65%. This very high solids content reduces transportation costs and increases the coating thickness.

[0056] Of the total solids content, the base polymer makes up at least 40 wt%, at least 45 wt%, at least 50 wt%, or at least 55 wt% to at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 65 wt% or at most 60 wt%, including ranges defined by a lower and upper end point including from 40 to 80 wt%, 45 to 80 wt%, 50 to 80 wt%, 55 to 80 wt%, 40 to 75 wt%, 45 to 75 wt%, 50 to 75 wt%, 55 to 75 wt%, 40 to 70 wt%, 45 to 70 wt%, 50 to 70 wt%, 55 to 70 wt%, 40 to 65 wt%, 45 to 65 wt%, 50 to 65 wt%, 55 to 65 wt%, 40 to 60 wt%, 45 to 60 wt%, 50 to 60 wt%, or 55 to 60 wt%.

[0057] Of the total solids content, the bio-based component makes up at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt% to at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 35 wt%, , including ranges defined by a lower and upper end Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) point including from 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, 15 to 45 wt%, 20 to 45 wt%, 25 to 45 wt%, 30 to 45 wt%, 35 to 45 wt%, 15 to 40 wt%, 20 to 40 wt%, 25 to 40 wt%, 30 to 40 wt%, 35 to 40 wt%, 15 to 35 wt%, 20 to 35 wt%, 25 to 35 wt%, and 30 to 35 wt%.

[0058] The adhesive composition of the present invention can be formulated in various forms, such as liquids, pastes, films, depending on the desired application method. The adhesive is designed to be easily applied to the substrates to be bonded, either manually or through automated dispensing equipment. Upon application, the adhesive cures at ambient temperatures, forming a strong and lasting bond between the substrates.

[0059] Additives

[0060] The adhesive 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. .

[0061] Where the adhesive composition contains one or more additives, the additives may be added at any step in the preparation thereof including being added with or pre-mixed with any of the primary components.

[0062] Where the additive is a solvent it is different than the solvent in the primary composition. In this case, the solvent may be, but is not limited to, alcohols such as ethanol or methanol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide. The solvent is generally added in an amount and type to assist in the dissolution Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) 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.

[0063] 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.

[0064] 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.

[0065] The inclusion of a plasticizer may help control the viscosity of the adhesive and improve flexibility.

[0066] The inclusion of a stabilizer may help enhance the shelf life and / or the heat resistance of the adhesive. An exemplary antimicrobial agent is a 2: 1 blend of emulsified water-based silver solution and zinc-pyrithione.

[0067] 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 adhesive composition. Pigments may be in the form of solids or a dispersion in a resin carrier.

[0068] Reinforcements (e.g., flake or milled glass and / or fumed silica), may be used to impart certain properties. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0069] The adhesive composition may be a curable composition that includes curing agent / hardener component in addition to the adhesive composition or as part of the adhesive composition. The amount of the hardener component used may vary depending on whether the hardener component is used in addition to or as part of the adhesive 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.

[0070] The additives addition amount will vary depending upon the end use. In an embodiment, the total amount of all additives (based on the total of the adhesive 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%.

[0071] Other exemplary additives and amounts include:

[0072] 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%.

[0073] 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%.

[0074] 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%.

[0075] 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-

[0076] Ob er Schwandorf, 1976, pp. 237-398. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0077] Kits

[0078] The present invention includes an embodiment where a kit is provided such that the adhesive composition described above is present together with instructions for preparing and / or using the adhesive composition.

[0079] In the kits of the present invention, additives may be present. In an embodiment the additives are present in the adhesive composition. Alternatively, the additives may be contained in their own separate container(s) for addition as applicable to the desired use. For example, dyes and / or pigments may be stored in a separate container in the kit.

[0080] Storage temperatures for the kit should be 45° to 90°F, 55° to 85°F, or 60° to 80°F. Freezing temperatures, direct sunlight, & moisture should be avoided. Further, the kit should not be exposed to direct heat and / or should be kept away from heat sources.

[0081] In an embodiment, the adhesive composition is contained in a delivery device. In an embodiment the delivery device may contain the adhesive composition and a curing agent in separate chambers of a delivery device, wherein each container is connected to a mixing chamber by way of a tube, a channel, or other delivery vehicle.

[0082] In an embodiment, the delivery device further comprises a tip, tube, channel or other outlet for application of the adhesive to the desired surface.

[0083] Method of Preparing an Adhesive Composition

[0084] In an embodiment, the adhesive composition is prepared by: stirring, shaking, or agitating a bio-based component, a base polymer, a zinc-containing compound, and a solvent that has low or is free from volatile organic compounds for a time and under conditions sufficient to blend the base polymer, the bio-based component, and the zinc-containing compound in the solvent to substantial homogeneity thus forming the adhesive composition. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0085] In an embodiment the method further comprising adding one or more additive selected from the group consisting of a promoter, defoamer, a thickener, a rheology modifier, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

[0086] In an embodiment, the bio-based component, the base polymer, the zinc-containing compound, the solvent, and, optional, additive, may be added in any order. In an embodiment, all components are added and the mixture is then stirred, shaken, or agitated.

[0087] In an embodiment, the bio-based component or the base polymer are first added to the solvent and the mixture is then stirred, shaken, or agitated for a time and under conditions suitable to fully disperse the base polymer or bio-based component in the solvent. Then, to this mixture, the other of the base polymer or the bio-based component is added and the resulting mixture is stirred, shaken, or agitated for a time and under conditions suitable to fully disperse the bio-based component and base polymer in the solvent to substantial homogeneity thus forming the adhesive composition. The zinc-containing compound may be added together with the bio-based component or the base polymer, may be added prior to the bio-based component and the base polymer, may be added after the bio-based component and the base polymer, or may be added between the bio-based component and the base polymer.

[0088] In a variant of the method, a portion of the bio-based component, the base polymer and / or the zinc-containing compound may be mixed with the solvent with the remainder added following a first interval of stirring, shaking, or agitating.

[0089] The time and conditions for stirring, shaking, or agitating (i.e., mixing) is not particularly limited so long as it is sufficient to ensure that the bio-based component, the base polymer and the zinc-containing compound, respectively, are fully dispersed in the solvent. The time and conditions would be understood to the skilled artisan. Exemplary, times are Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) from 15 seconds to 5 minutes, from 30 seconds to 4 minutes, from 1 minute to 3 minutes.

[0090] Stirring can be accomplished by using a jiffy blade mixer at a slow speed (e.g., 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm). Alternatively, hand shaking or agitation may be used.

[0091] “Substantially homogeneity” in this context means that the base polymer, the biobased component, and / or the zinc-containing compound are mixed well and in a manner that permits creation of an approximately uniform dispersion. In an embodiment, the total mixing time is from 30 seconds to 5 minutes, from 1 minute to 4 minutes, from 2 minutes to 3 minutes.

[0092] In the preparation method above, the adhesive composition may optionally be allowed stand for a time ranging from 30 seconds to 5 minutes, from 1 minute to 4 minutes, from 2 minutes to 3 minutes prior to being applied to a surface of a material.

[0093] In an embodiment, the adhesive composition has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.05 wt%, less than 0.01 wt% total VOCs.

[0094] In an embodiment, the adhesive composition has no detectable odor after mixing.

[0095] In an embodiment, the adhesive composition has a pH after mixing ranging from 4.0 to 8.0, from 4.5 to 8.0, from 5.0 to 8.0, from 5.5 to 8.0, from 6.0 to 8.0, from 6.5 to 7.5, from 6.7 to 7.3, from 6.9 to 7.1.

[0096] In an embodiment, the adhesive composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps. As a lower viscosity limit, at least 1,000 cps, at least 1,500 cps, at least 2,000 cps, at least 2,500 cps, at least 3,000 cps, at least 3,500 cps, at least 4,000 cps, at least 4,500 cps, at least 5,000 cps, at least 7,500 cps, at least 10,000 cps, at least 12,500 cps at least 15,000 cps, at least 17,500 cps, and at least 20,000 cps are mentioned. As an upper viscosity limit, at most 30,000 cps, at most 27,500 cps, at most 25,000 cps, at most 22,500 cps, at most 20,000 cps, at most 17,500 cps, at most 15,000 cps, at most 12,500 cps, at most Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0097] 10,000 cps, at most 7,500 cps, at most 5,000 cps, at most 3,500 cps, at most 3,000 cps, at most 2,500 cps, at and at most 2,000 cps are mentioned. Ranges and sub-ranges based on a selection of a lower limit and an upper limit from the foregoing are mentioned. Exemplary viscosity ranges include formulations having a viscosity of 1,000 to 30,000 cps, 2,500 to 30,000 cps, 5,000 to 30,000 cps, 7,500 to 30,000 cps, 10,000 to 30,000 cps, 12,500 to 30,000 cps, 15,000 to 30,000 cps, 17,500 to 30,000 cps, 20,000 to 30,000 cps, 1,000 to 25,000 cps,

[0098] 2,500 to 25,000 cps, 5,000 to 25,000 cps, 7,500 to 25,000 cps, 10,000 to 25,000 cps, 12,500 to 25,000 cps, 15,000 to 25,000 cps, 17,500 to 25,000 cps, 20,000 to 25,000 cps, 1,000 to 20,000 cps, 2,500 to 20,000 cps, 5,000 to 20,000 cps, 7,500 to 20,000 cps, 10,000 to 20,000 cps, 12,500 to 20,000 cps, 15,000 to 20,000 cps, 17,500 to 20,000 cps, 1,000 to 15,000 cps,

[0099] 2,500 to 15,000 cps, 5,000 to 15,000 cps, 7,500 to 15,000 cps, 10,000 to 15,000 cps, 12,500 to 15,000 cps, 1,000 to 10,000 cps, 1,500 to 10,000 cps, 2,000 to 10,000 cps, 2,500 to 10,000 cps, 3,000 to 10,000 cps, 3,500 to 10,000 cps, 4,000 to 10,000 cps, 4,500 to 10,000 cps, 5,000 to 10,000 cps, 7,500 to 10,000 cps, 1,000 to 7,500 cps, 1,500 to 7,500 cps, 2,000 to 7,500 cps,

[0100] 2,500 to 7,500 cps, 3,000 to 7,500 cps, 3,500 to 7,500 cps, 4,000 to 7,500 cps, 4,500 to 7,500 cps, 5,000 to 7,500 cps, 1,000 to 5,000 cps, 1,500 to 5,000 cps, 2,000 to 5,000 cps, 2,500 to 5,000 cps, 3,000 to 5,000 cps, 3,500 to 5,000 cps, and 4,000 to 5,000 cps.

[0101] The adhesive 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%, or at least 60 wt% of bio-based materials (e.g., a plant-based and / or biorenewable polymer). The adhesive composition contains a total of 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 bio-renewable materials). In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) an upper (i.e., “at most”) limit from those selected above. Exemplary ranges include: 24 wt% to 95 wt%, 30 wt% to 95 wt%, 35 wt% to 95 wt%, 40 wt% to 95 wt%, 24 wt% to 85 wt%, 30 wt% to 85 wt%, 35 wt% to 85 wt%, 40 wt% to 85 wt%, 24 wt% to 75 wt%, 30 wt% to 75 wt%, 35 wt% to 75 wt%, 40 wt% to 75 wt%, 24 wt% to 65 wt%, 30 wt% to 65 wt%, 35 wt% to 65 wt%, 40 wt% to 65 wt%, 24 wt% to 50 wt%, 30 wt% to 50 wt%, 35 wt% to 50 wt%, 40 wt% to 50 wt%, 24 wt% to 40 wt%, 30 wt% to 40 wt%, 35 wt% to 40 wt%, 24 wt% to 35 wt%, 25 wt% to 35 wt%, and 27.5 wt% to 35 wt%.

[0102] In an embodiment, after mixing, the adhesive 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%, or over 90%, over 95%, over 98%, or over 99% for example from 50 to 98%, from 55 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 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 35 to 80%, from 40 to 70%, from 45 to 65%. This very high solids content reduces transportation costs and increases the coating thickness.

[0103] Of the total solids content, the base polymer makes up at least 40 wt%, at least 45 wt%, at least 50 wt%, or at least 55 wt% to at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 65 wt% or at most 60 wt%, including ranges defined by a lower and upper end point including from 40 to 80 wt%, 45 to 80 wt%, 50 to 80 wt%, 55 to 80 wt%, 40 to 75 wt%, 45 to 75 wt%, 50 to 75 wt%, 55 to 75 wt%, 40 to 70 wt%, 45 to 70 wt%, 50 to 70 wt%, 55 to 70 wt%, 40 to 65 wt%, 45 to 65 wt%, 50 to 65 wt%, 55 to 65 wt%, 40 to 60 wt%, 45 to 60 wt%, 50 to 60 wt%, or 55 to 60 wt%.

[0104] Of the total solids content, the bio-based component makes up at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt% to at most 50 wt%, at most 45 Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) wt%, at most 40 wt%, at most 35 wt%, including ranges defined by a lower and upper end point including from 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, 15 to 45 wt%, 20 to 45 wt%, 25 to 45 wt%, 30 to 45 wt%, 35 to 45 wt%, 15 to 40 wt%, 20 to 40 wt%, 25 to 40 wt%, 30 to 40 wt%, 35 to 40 wt%, 15 to 35 wt%, 20 to 35 wt%, 25 to 35 wt%, and 30 to 35 wt%.

[0105] Depending upon the surface to be treated, the application method, and the desired application thickness, among other factors, the adhesive composition of the present invention may be diluted by up to 50% (i.e., add an equal amount of solvent to the volume of the mixed adhesive composition), up to 40%, up to 30%, up to 25%, up to 20%, up to 15%, or up to 10% with a solvent. In this regard, there would be a corresponding decrease in the solids content of the adhesive composition to be applied. The solvent for dissolution may be water.

[0106] The adhesive composition of the present invention may be applied directly to a surface of a material.

[0107] Method of Using the Adhesive Composition and Resulting Material Construct

[0108] In an embodiment is a method of adhering a surface of a first material to a surface of second material by:

[0109] (1) applying a layer of an adhesive composition comprising a bio-based component, a base polymer, a zinc-containing compound, a solvent that has low or is free from volatile organic compounds, and, optionally, one or more additives 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 (e.g., cardboard), composites, textile and plastic, and

[0110] (2) contacting the surface of the first material to the surface of the second surface; and

[0111] (3) allowing the adhesive composition to cure. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0112] In the foregoing methods, application thickness will vary based upon the materials to be adhered, the adherence strength desired, the adhesive composition viscosity, the adhesive composition solids content, and whether a catalyst is included. 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). In an embodiment, application thickness ranges from 0.1 to 0.5 inches (100 - 500 mils), from 0.15 to 0.45 inches (150 -450 mils), from 0.2 to 0.4 inches (200 - 400 mils), from 0.25 to 0.35 inches (250 - 350 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.

[0113] The adhesive composition may be applied to the surface of a material by brushing, rolling, or spraying.

[0114] Following contacting of the two surfaces of the materials, the adhesive composition of the present invention has a curing / dry-time ranging from 2 to 15 hours, from 3 to 14 hours, from 4 to 13 hours, from 5 to 12 hours, from 6 to 11 hours, or from 7 to 10 hours, but the drying time varies depending upon the temperature, ventilation, and catalyst system being used. For example, the drying time at ambient temperature may be 8 hours or less.

[0115] The curing in step (3) may be with constant or intermittent pressure to maintain contact between the first and second surfaces for the full curing time or until the two surfaces remain adhered to each other without application of pressure.

[0116] After preparing the adhesive composition, a process for curing the composition may be used to form a thermoset or cured composition. For example, the composition or formulation may be cured under conventional processing conditions to form an adhesive bond. Curing the adhesive composition may be carried out at curing reaction conditions including a predetermined temperature and for a predetermined period of time sufficient to Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) cure the composition. The curing conditions may be dependent on the various components used in the curable composition such as the hardener used in the formulation. The curing reaction conditions include, e.g., carrying out the reaction under a temperature, generally in the range of from -5° C. to 60° C. (e.g., 0° C. to 50° C., 5° C. to 45° C., 10° C. to 35° C., 15° C. to 30° C., 20° C. to 27.5° C. etc.), including ambient temperature. For sprayable applications, the adhesive may be applied to substrates, e.g., using airless sprayers and airassisted pneumatic sprayers and the like. The applied composition may be cured by heating the composition at the aforementioned curing temperatures.

[0117] Temperature and humidity directly affect pot life and dry time. Accordingly, in an embodiment the conditions should be between 40 - 95 °F, between 50 and 85 °F, between 60 and 80 °F, or between 65 and 75 °F and the humidity should not exceed 80%, not exceed 70%, not exceed 60%, or not exceed 50%.

[0118] 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.

[0119] Prior to application of the adhesive composition to a surface(s), the surface(s) may pretreated and / or cleaned.

[0120] In an embodiment, the surface(s) to be adhered may be cleaned prior to application of the adhesive composition. 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.

[0121] 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, bee holes, masonry surface defects and openings such as conduits, pipes, drains, door frames, vents, air Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) conditioner openings, electrical openings, control joints, or any dissimilar materials should be repaired using urethane or other approved patching.

[0122] Another form of surface pretreatment envisioned in the present invention includes fluting, scoring, sandblasting, and / or etching as well as raking joints.

[0123] In an embodiment, the adhesive composition 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 adhesive composition 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 adhesive composition would be adversely affective if relative humidity is greater than 90% and, therefore, it should be avoided.

[0124] In the case of spills or following application excess adhesive composition can be cleaned up with water.

[0125] Material Constructs / Products

[0126] The adhesive 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. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0127] The adhesive composition is suitable for and has excellent adherence properties with a broad scope of materials including asphalt, ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging (e.g., cardboard), composites, textile and plastic. Further, the adhesive composition is suitable for and has excellent adherence properties when two different materials are used.

[0128] Thus, within the scope of the present invention is a material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises a cured product of a bio-based component, a base polymer, a zinc-containing compound, and a solvent that has low or is free from volatile organic compounds and has at least 24 wt% of the bio-based component based on the total solids content of the adhesive.

[0129] Benefits of Adhesive

[0130] In some embodiments, the adhesive composition of the present invention provides one or more of the following advantages over conventional starch adhesives :

[0131] • Enhanced Adhesive Properties: The addition of the base polymer (e.g., PVA) and a zinc-containing compound significantly improves the bond strength, water resistance, and microbial resistance of the adhesive.

[0132] • Low Cost: The use of starch as the primary component makes the adhesive cost-effective.

[0133] • Renewability and Biodegradability: The adhesive is based on renewable resources and is biodegradable, making it environmentally friendly.

[0134] Exemplary embodiments of the present invention include:

[0135] [1] An adhesive composition comprising: a bio-based component; Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) a base polymer; a zinc-containing compound; and a solvent that has low or is free from volatile organic compounds.

[0136] [2] The adhesive composition of [1], wherein the base polymer is a polyvinyl alcohol.

[0137] [3] The adhesive composition of [1] or [2], wherein the adhesive composition comprises from 35 to 85 wt% of the base polymer.

[0138] [4] The adhesive composition of any one of [1] - [3], wherein the bio-based component is a starch.

[0139] [5] The adhesive composition of any one of [1] - [4], wherein the bio-based component is com starch.

[0140] [6] The adhesive composition of any one of [1] - [5], wherein the bio-based component is potato starch.

[0141] [7] The adhesive composition of any one of [1] - [6], wherein the adhesive composition comprises from 5 to 40 wt% of the bio-based component.

[0142] [8] The adhesive composition of any one of [1] - [7], wherein the solvent is free from VOCs.

[0143] [9] The adhesive composition of any one of [1] - [8], wherein the solvent is water.

[0144]

[0010] The adhesive composition of any one of [1] - [9], wherein the adhesive composition comprises from 1 to 25 wt% of the solvent.

[0145]

[0011] The adhesive composition of any one of [1] -

[0010] , wherein the composition has a pH ranging from 4.0 to 8.0.

[0146]

[0012] The adhesive composition of any one of [1] -

[0011] , wherein the composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0147]

[0013] The adhesive composition of any one of [1] -

[0012] , wherein the zinc-containing compound is at least one selected from the group consisting of zinc oxide, zinc chloride, and zinc sulfate.

[0148]

[0014] The adhesive composition of any one of [1] -

[0013] , wherein the zinc-containing compound is zinc chloride.

[0149]

[0015] The adhesive composition of any one of [1] -

[0014] , wherein the adhesive composition comprises from 0.25 to 10 wt% of the zinc-containing compound.

[0150]

[0016] The adhesive composition of any one of [1] -

[0015] , further comprising an additive and said additive is one or more 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

[0151]

[0017] A kit comprising, the adhesive composition of any one of [1] -

[0016] together with instructions for use thereof.

[0152]

[0018] The kit of

[0017] , further comprising one or more separately packaged additives 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

[0153]

[0019] The kit of

[0017] or

[0018] , wherein the adhesive composition is contained in a delivery device. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0154]

[0020] A method of making an adhesive composition, comprising stirring, shaking, or agitating a bio-based component, a base polymer, a zinc- containing compound, and a solvent that has low or is free from volatile organic compounds for a time and under conditions sufficient to blend the base polymer and the bio-based component in the solvent to substantial homogeneity thus forming the adhesive composition.

[0155]

[0021] The method of

[0020] , wherein the base polymer is a polyvinyl alcohol.

[0156]

[0022] The method of

[0020] or

[0021] , wherein the adhesive composition comprises from 35 to 85 wt% of the base polymer.

[0157]

[0023] The method of any one of

[0020] -

[0022] , wherein the bio-based component is a starch.

[0158]

[0024] The method of any one of

[0020] -

[0023] , wherein the bio-based component is com starch.

[0159]

[0025] The method of any one of

[0020] -

[0024] , wherein the bio-based component is potato starch.

[0160]

[0026] The method of any one of

[0020] -

[0025] , wherein the adhesive composition comprises from 5 to 40 wt% of the bio-based component.

[0161]

[0027] The method of any one of

[0020] -

[0026] , wherein the solvent is free from VOCs.

[0162]

[0028] The method of any one of

[0020] -

[0027] , wherein the solvent is water.

[0163]

[0029] The method of any one of

[0020] -

[0028] , wherein the adhesive composition comprises from 1 to 25 wt% of the solvent.

[0164]

[0030] The method of any one of

[0020] -

[0029] , wherein the composition has a pH ranging from 4.0 to 8.0.

[0165]

[0031] The method of any one of

[0020] -

[0030] , wherein the composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0166]

[0032] The method of any one of

[0020] -

[0031] , wherein the zinc-containing compound is at least one selected from the group consisting of zinc oxide, zinc chloride, and zinc sulfate.

[0167]

[0033] The method of any one of

[0020] -

[0032] , wherein the zinc-containing compound is zinc chloride.

[0168]

[0034] The method of any one of

[0020] -

[0033] , wherein the adhesive composition comprises from 0.25 to 10 wt% of the zinc-containing compound.

[0169]

[0035] The method of any one of

[0020] -

[0034] , further comprising an additive and said additive is one or more 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

[0170]

[0036] A method of adhering a surface of a first material to a surface of second material comprising:

[0171] (1) applying a layer of an adhesive composition comprising a bio-based component, a base polymer, a zinc-containing compound, a solvent that has low or is free from volatile organic compounds, and, optionally, one or more additives 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

[0172] (2) contacting the surface of the first material to the surface of the second surface; and

[0173] (3) allowing the adhesive composition to cure.

[0174]

[0037] The method of

[0036] , wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0175]

[0038] The method of

[0036] or

[0037] , wherein said allowing the adhesive composition to cure is at ambient temperature.

[0176]

[0039] The method of any one of

[0036] -

[0038] , wherein the base polymer is a polyvinyl alcohol.

[0177]

[0040] The method of any one of

[0036] -

[0039] , wherein the adhesive composition comprises from 35 to 85 wt% of the base polymer.

[0178]

[0041] The method of any one of

[0036] -

[0040] , wherein the bio-based component is a starch.

[0179]

[0042] The method of any one of

[0036] -

[0041] , wherein the bio-based component is com starch.

[0180]

[0043] The method of any one of

[0036] -

[0042] , wherein the bio-based component is potato starch.

[0181]

[0044] The method of any one of

[0036] -

[0043] , wherein the adhesive composition comprises from 5 to 40 wt% of the bio-based component.

[0182]

[0045] The method of any one of

[0036] -

[0044] , wherein the solvent is free from VOCs.

[0183]

[0046] The method of any one of

[0036] -

[0045] , wherein the solvent is water.

[0184]

[0047] The method of any one of

[0036] -

[0046] , wherein the adhesive composition comprises from 1 to 25 wt% of the solvent.

[0185]

[0048] The method of any one of

[0036] -

[0047] , wherein the composition has a pH ranging from 4.0 to 8.0.

[0186]

[0049] The method of any one of

[0036] -

[0048] , wherein the composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps.

[0187]

[0050] The method of any one of

[0036] -

[0049] , wherein the zinc-containing compound is at least one selected from the group consisting of zinc oxide, zinc chloride, and zinc sulfate. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0188]

[0051] The method of any one of

[0036] -

[0050] , wherein the zinc-containing compound is zinc chloride.

[0189]

[0052] The method of any one of

[0036] -

[0051] , wherein the adhesive composition comprises from 0.25 to 10 wt% of the zinc-containing compound.

[0190]

[0053] The method of any one of

[0036] -

[0052] , further comprising an additive and said additive is one or more 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

[0191]

[0054] A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises a cured product of a bio-based component, a base polymer, a zinc-containing compound, and a solvent that has low or is free from volatile organic compounds and has at least 24 wt% of the bio-based component based on the total solids content of the adhesive.

[0192]

[0055] The material construct of

[0054] , wherein the materials may be the same or different materials and are selected from the group consisting of asphalt, ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0193]

[0056] The material construct of

[0054] or

[0055] , wherein the base polymer is a polyvinyl alcohol.

[0194]

[0057] The material construct of any one of

[0054] -

[0056] , wherein the adhesive composition comprises from 35 to 85 wt% of the base polymer. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0195]

[0058] The material construct of any one of

[0054] -

[0057] , wherein the bio-based component is a starch.

[0196]

[0059] The material construct of any one of

[0054] -

[0058] , wherein the bio-based component is com starch.

[0197]

[0060] The material construct of any one of

[0054] -

[0059] , wherein the bio-based component is potato starch.

[0198]

[0061] The material construct of any one of

[0054] -

[0060] , wherein the adhesive composition comprises from 5 to 40 wt% of the bio-based component.

[0199]

[0062] The material construct of any one of

[0054] -

[0061] , wherein the solvent is free from VOCs.

[0200]

[0063] The material construct of any one of

[0054] -

[0062] , wherein the solvent is water.

[0201]

[0064] The material construct of any one of

[0054] -

[0063] , wherein the adhesive composition comprises from 1 to 25 wt% of the solvent.

[0202]

[0065] The material construct of any one of

[0054] -

[0064] , wherein the composition has a pH ranging from 4.0 to 8.0.

[0203]

[0066] The material construct of any one of

[0054] -

[0065] , wherein the composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps.

[0204]

[0067] The material construct of any one of

[0054] -

[0066] , wherein the zinc-containing compound is at least one selected from the group consisting of zinc oxide, zinc chloride, and zinc sulfate.

[0205]

[0068] The material construct of any one of

[0054] -

[0067] , wherein the zinc-containing compound is zinc chloride.

[0206]

[0069] The material construct of any one of

[0054] -

[0068] , the adhesive composition comprises from 0.25 to 10 wt% of the zinc-containing compound. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0207]

[0070] The material construct of any one of

[0054] -

[0069] , further comprising an additive and said additive is one or more 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

[0208] 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.

[0209] 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.

[0210] 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 disclosed herein.

[0211] Except where expressly noted, trademarks are shown in upper case.

[0212] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight. Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0213] 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.

[0214] 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.

[0215] 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. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.

[0216] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive 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.

[0217] 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 Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) 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.

[0218] 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’.

[0219] 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.

[0220] 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). Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)

[0221] 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.

[0222] 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.

[0223] As used herein, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials.

[0224] 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.

[0225] 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.

[0226] 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 Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO) embodiments and applications without departing from the spirit and scope of the invention.

[0227] 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.

[0228] 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 / 66 (BIOB- 19 / 01 WO)CLAIMSWhat we claim is1. An adhesive composition comprising:5 to 40 wt% of a bio-based component;35 to 85 wt% of the base polymer of a base polymer;0.25 to 10 wt% of a zinc-containing compound; and1 to 25 wt% of a solvent that has low or is free from volatile organic compounds.

2. The adhesive composition of claim 1, wherein the base polymer is a polyvinyl alcohol.

3. The adhesive composition of claim 1, wherein the bio-based component is a starch.

4. The adhesive composition of claim 3, wherein the bio-based component is com starch or a potato starch.

5. The adhesive composition of claim 1, wherein the composition has a pH ranging from 4.0 to 8.0.

6. The adhesive composition of claim 1, wherein the composition has a dynamic viscosity at 25°C ranging from 1,000 to 30,000 cps.

7. The adhesive composition of claim 1, wherein the zinc-containing compound is at least one selected from the group consisting of zinc oxide, zinc chloride, and zinc sulfate.Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)8. The adhesive composition of claim 1, further comprising an additive and said additive is one or more 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, a UV light stabilizer, an antioxidant, an air release agent, an adhesion promoter, and a crosslinker.

9. A method of making an adhesive composition of claim 1, comprising stirring, shaking, or agitating the bio-based component, the base polymer, the zinc- containing compound, and the solvent for a time and under conditions sufficient to blend the base polymer and the bio-based component in the solvent to substantial homogeneity thus forming the adhesive composition.

10. A method of adhering a surface of a first material to a surface of second material comprising:(1) applying a layer of an adhesive composition of claim 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(2) contacting the surface of the first material to the surface of the second surface; and(3) allowing the adhesive composition to cure.

11. The method of claim 10, wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.Attorney Docket No. 40787 / 66 (BIOB- 19 / 01 WO)12. The method of claim 10, wherein said allowing the adhesive composition to cure is at ambient temperature.

13. A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises a cured product of the adhesive composition of claim 1 wherein said adhesive composition has at least 24 wt% of the bio-based component based on the total solids content of the adhesive.

14. The material construct of claim 13, wherein the materials may be the same or different materials and are selected from the group consisting of asphalt, ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

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