Bio-based binder composition and preparation method therefor

Abstract

This invention provides a bio-based binder composition and preparation method therefor. In one embodiment, said bio-based binder composition comprises: a) 0.01 to 60 wt.% of a polyphenol; b) 0.5 to 90 wt.% of a first bio-based polymer, comprising multiple amino or hydroxyl groups as first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; c) 0.5 to 90 wt.% of a second bio-based polymer; d) 0.01 to 50 wt.% of a metallic compound, said metallic compound is selected from the group consisting of aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), sodium (I) and zinc(II) compounds; and e) 1 to 99 wt.% of a protic solvent; wherein said bio-based binder composition can be adjusted to a condition for forming a transparent polymeric network cross-linked by covalent and non-covalent interactions.

Description

BIO-BASED BINDER COMPOSITION AND PREPARATION METHOD THEREFORFIELD OF THE INVENTION

[0001] The present invention relates to bio-based binders and their preparation methods.BACKGROUND OF THE INVENTION

[0002] Binder is a substrate or molecule that allowing the connection between two materials or two reacting sites in terms of molecular level. The term “binder” is often mixed with “adhesive”, which is any substance that can bind two materials together while resisting the separation from external force. In fact, adhesion is only one of the applications that binder provides. By definition, adhesive is a substance, such as glue, that provides or promotes adhesion while binder is a substance that causes two other substances to form into one, for example, pigment printing incorporates a binder with the pigments in the paste formulation.

[0003] Various applications of adhesive binder were developed in the recent decades. Glue is used for sticking two surfaces or materials together, such as paper, glass surface or construction work with wood or metal. The adhesives used are based on how strong the application required. For instance, the cellulose-cellulose connection between starch glue and paper is just enough for daily work with little to none hazard and easy handling. On the other hand, the harmful super glue (AA glue), often used connect in wood and glass, contains methyl 2-cyanoacrylate which can irritate and bum the skin and eyes, also irritate the nose and throat causing coughing and wheezing. (Methyl 2-cyanoacrylate Hazardous Substance Fact Sheet, 2000) The massive adhesive force is due to the strong covalent bonding from the alpha-cyanoacrylate and the material it attached to, comparing to the relatively weaker hydrogen bond that used in starch glue or white polyvinyl acetate (PVAc) glue.

[0004] Traditional binders contain compounds / chemicals which are flammable and / or hazardous to health as shown in Acrylic glue-safety data sheet, 2016, Polyurethane contact adhesive-safety data sheet, 2012 and Styrene adhesive-safety data sheet, 2018. .

[0005] Binder also stands in crucial part in surgical repair and wound closure. The bio-adhesive binder was able to overcome the contour tissue surface with great cross-linked network. (Liu, et al., 2017) Also those bio-adhesives might contribute to reduce the chance of infection while increasing the efficacy of the therapeutic drug. (Pinnaratip, Bhuiyan, Meyers, Rajachar, & Lee, 2019) As a bio-adhesive, the binder is expected to use in the presence of water and blood,sometime sweat as well. Therefore, it is necessary to achieve strong adhesion while in wet or aqueous condition.

[0006] Patents US20210207008A1 and CN113088243A disclose a catechol-containing polymeric additive and its application in polymer adhesives and sealants for a variety of applications on dry and wet surfaces. The invention was inspired by the protein produced from the byssus of mussels containing a high content of catechol groups. The adhesive comprises a first component (polysiloxane or polyurethane adhesive) and a second component (catecholcontaining polymer additive). The catechol-containing polymer additive of the described polymer adhesive is a reaction product of polyvinylpyrrolidone (PVP) (a synthetic polymer from petroleum resources) and 3’,4’-dihydroxy-2-chloroacetophenone (a reaction product of pyrocatechol and chloroacetic acid).

[0007] Patent US2018 / 0256777A1 discloses an adhesive for underwater adhesion with a polymer core which is a 4-arm, 6-arm, or 8-arm polyethylene oxide) substituted with at least one L-3,4-dihydroxyphenylalanine (L-DOPA) group and at least one sulfhydryl -reactive group. Harmful chemicals including acetone and dichloromethane are used in the synthesis of the described adhesive.

[0008] Patent US8916652B2 discloses a multi-armed catechol compound blends obtained by chemical syntheses from polyethylene glycol) and multihydroxy phenyl derivatives. However the syntheses involve harmful chemicals including chloroform, DMF, etc.

[0009] Patent WO 2023 / 114321 Al discloses bio-based adhesives suitable for wet surfaces and underwater. The described underwater adhesive composition comprising (i) a zein, (ii) a tannic acid, (iii) an inorganic filler, and (iv) a natural polymer (a protein or a polysaccharide), wherein the composition comprises about 30-80 wt% of tannic acid. The adhesive composition can further comprise FeCh. The described adhesive is amber-colored due to the high content of zein and tannic acid used. Preparation of the described adhesive simply involves dissolution and mixing the components in solvent (ethanol and water). No heat is required. The patent does not mention the type of interactions involved in the adhesive, but it is unlikely to have covalent bond formation because of the preparation method of the adhesive.

[0010] The present invention provides a binder which tackle the above problems associated with the existing binders.SUMMARY OF THE INVENTION

[0011] This invention provides a bio-based binder composition. In one embodiment, said biobased binder composition comprises: a) 0.01 to 60 wt.% of a polyphenol; b) 0.5 to 90 wt.% ofa first bio-based polymer, comprising multiple amino or hydroxyl groups as first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; c) 0.5 to 90 wt.% of a second bio-based polymer; d) 0.01 to 50 wt.% of a metallic compound, said metallic compound is selected from the group consisting of aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), sodium (I) and zinc(II) compounds; and e) 1 to 99 wt.% of aprotic solvent; wherein said bio-based binder composition can be adjusted to a condition for forming a transparent polymeric network cross-linked by covalent and non-covalent interactions.

[0012] This invention also provides an article comprising a substrate coated with the bio-based binder composition of this invention.

[0013] This invention also provide a method of preparing the bio-based binder of this invention. In one embodiment, said method comprises the steps of: a) Providing a bio-based binder composition comprising: i) 0.01 to 60 wt.% of a polyphenol; ii) 0.5 to 90 wt.% of a first biobased polymer, comprising multiple first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; iii) 0.5 to 90 wt.% of a second bio-based polymer; iv) 0.01 to 50 wt.% of a metallic compound; and v) 1 to 99 wt.% of a protic solvent; b) Dissolving said bio-based binder composition at 15 to 95°C and oxidizing said polyphenol to form a first solution; c) Adjusting said first solution to a pH value favorable for said first Michael addition reaction to form a second solution; and d) Adjusting said second solution to a suitable pH value to form said bio-based binder.BRIEF DESCRIPTION OF THE FIGURES

[0014] A full and enabling disclosure of the present invention, including the best mode thereof, directed to one of ordinary skill in the art, is set forth more particularly in the remainder of the specification, which makes reference to the appended figures in which:

[0015] Figure 1 illustrates an exemplary process for preparing and applying the binder composition.DETAILED DESCRIPTION OF THE INVENTION

[0016] This invention provides a bio-based binder composition. In one embodiment, said biobased binder composition comprises: a) 0.01 to 60 wt.% of a polyphenol; b) 0.5 to 90 wt.% of a first bio-based polymer, comprising multiple amino or hydroxyl groups as first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; c) 0.5 to 90 wt.% of a second bio-based polymer; d) 0.01 to 50 wt.% of ametallic compound, said metallic compound is selected from the group consisting of aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), sodium (I) and zinc(II) compounds; and e) 1 to 99 wt.% of aprotic solvent; wherein said bio-based binder composition can be adjusted to a condition for forming a transparent polymeric network cross-linked by covalent and non-covalent interactions.

[0017] In one embodiment, said first Michael donors comprises both amino groups and hydroxyl groups.

[0018] In one embodiment, said second bio-based polymer comprises multiple amino or hydroxyl groups as second Michael donors for a second Michael addition reaction with a second Michael acceptor formed by oxidation of said polyphenol.

[0019] In one embodiment, said second Michael donors are amino groups or hydroxyl groups different from said first Michael donors.

[0020] In one embodiment, said polyphenol comprises one or more of tannic acid, tannins, phenolic acids, flavonoids, lignin, lignans, or stilbenes; said first bio-based polymer or second bio-based polymer comprises one or more of cellulose, poly(vinyl alcohol), chitosan, or gelatin; or said protic solvent comprises water or alcohol.

[0021] In one embodiment, said condition comprises dissolving said bio-based binder composition at a temperature at 15 to 95°C while oxidizing said polyphenol.

[0022] In one embodiment, said condition further comprises adjusting and maintaining at a suitable pH for said first or second Michael addition reaction.

[0023] In one embodiment, said condition further comprises adjusting pH to neutral and cooling to room temperature.

[0024] In one embodiment, said bio-based binder composition is a composition selected from the group consisting of: i) tannic acid, poly(vinyl alcohol), gelatin, aluminum chloride hexahydrate and water; ii) tannic acid, poly(vinyl alcohol), gelatin, calcium chloride and water; iii) tannic acid, poly(vinyl alcohol), gelatin, zinc chloride and water; and iv) tannic acid, poly(vinyl alcohol), gelatin, sodium chloride and water.

[0025] This invention also provides an article comprising a substrate coated with the bio-based binder composition of this invention.

[0026] In one embodiment, said substrate comprises synthetic or natural materials.

[0027] This invention also provide a method of preparing the bio-based binder of this invention. In one embodiment, said method comprises the steps of: a) Providing a bio-based binder composition comprising: i) 0.01 to 60 wt.% of a polyphenol; ii) 0.5 to 90 wt.% of a first biobased polymer, comprising multiple first Michael donors for a first Michael addition reactionwith a first Michael acceptor formed by oxidation of said polyphenol; iii) 0.5 to 90 wt.% of a second bio-based polymer; iv) 0.01 to 50 wt.% of a metallic compound; and v) 1 to 99 wt.% of a protic solvent; b) Dissolving said bio-based binder composition at 15 to 95°C and oxidizing said polyphenol to form a first solution; c) Adjusting said first solution to a pH value favorable for said first Michael addition reaction to form a second solution; and d) Adjusting said second solution to a suitable pH value to form said bio-based binder.

[0028] In one embodiment, said second bio-based polymer comprises multiple second Michael donors for a second Michael addition reaction with a second Michael acceptor formed by oxidation of said polyphenol and said step (c) further comprises adjusting said first solution to a pH value favorable for said second Michael addition reaction to form said second solution.

[0029] In one embodiment, said bio-based binder composition is a composition selected from the group consisting of: i) tannic acid, poly(vinyl alcohol), gelatin, aluminum chloride hexahydrate and water; ii) tannic acid, poly(vinyl alcohol), gelatin, calcium chloride and water; iii) tannic acid, poly(vinyl alcohol), gelatin, zinc chloride and water; and iv) tannic acid, poly(vinyl alcohol), gelatin, sodium chloride and water.

[0030] In one embodiment, said method further comprises one or more of the following steps: a) said temperature of step (b) is 80 to 90°C; b) said oxidizing at step (b) comprises air bubbling of said first solution; c) said pH value of step (c) is pH 7 to 10; d) said step (c) comprises further oxidizing said polyphenol; and e) said suitable pH value of step (d) is neutral.

[0031] Various embodiments of the present invention relate to a composition comprising at least (A) a polyphenol from natural resources including tannic acid, tannins, phenolic acids, flavonoids, lignin, lignans, stilbenes, etc.; (B) a first bio-based polymer, at least one polymer selected from i) a multiple amino groups containing polymer, or ii) a multiple hydroxyl groups containing polymer, or iii) a multiple amino groups and multiple hydroxyl groups containing polymer, examples: cellulose, poly(vinyl alcohol) from sugar cane alcohol, chitosan, gelatin, etc.; (C) a second bio-based polymer, at least one polymer selected from i) a multiple amino groups containing polymer, or ii) a multiple hydroxyl groups containing polymer, or iii) a multiple amino groups and multiple hydroxyl groups containing polymer, examples: cellulose, poly(vinyl alcohol) from sugar cane alcohol, chitosan, gelatin, etc. Selection criteria of a first polymer and a second polymer: i) at least the first polymer or the second polymer contains multiple amino groups for Michael addition with the oxidized polyphenol, or ii) both the first polymer and the second polymer contain multiple amino groups for Michael addition with the oxidized polyphenol but they are not the same, or iii) both the first polymer and the second polymer contain multiple hydroxyl groups and multiple amino groups simultaneously forMichael addition with the oxidized polyphenol but they are not the same; (D) a metallic compound including aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), zinc(II), etc.; (E) a solvent system including water and alcohol; In an embodiment, a binder composition, a coated substrate, and articles of manufacture employing the binder compositions and coated substrates as described herein.

[0032] This invention provides an advanced, bio-based, no formaldehyde release binder is developed by selection of raw materials from natural resources, using low energy consumption production process and non-toxic solvent system, resulting in a water resistant binder with good bonding performance on various substrates, pale in color, and odorless. The binder composition includes a polyphenol compound including (A) tannic acid, (B) a first polymer with multiple amino groups and / or multiple hydroxyl groups, (C) a second polymer with multiple amino groups and / or multiple hydroxyl groups, (D) a metallic compound, and (E) a solvent including water and alcohol.

[0033] In an embodiment, said binder composition comprises at least the following: (A) A polyphenol from natural resources including tannic acid, tannins, phenolic acids, flavonoids, lignin, lignans, stilbenes, etc. (B) A first bio-based polymer, at least one polymer selected from the following: (i) A multiple amino groups containing polymer; or (ii) A multiple hydroxyl groups containing polymer; or (iii) A multiple amino groups and multiple hydroxyl groups containing polymer; Example: cellulose, poly(vinyl alcohol), chitosan, gelatin, etc. (C) A second bio-based polymer, at least one polymer selected from the following: (i) A multiple amino group containing polymer; or (ii) A multiple hydroxyl group containing polymer; or (iii) A multiple amino group and multiple hydroxyl group containing polymer; Example: cellulose, poly(vinyl alcohol), chitosan, gelatin, etc. Selection criteria of a first polymer and a second polymer: (i) At least the first polymer or the second polymer contains multiple amino groups for Michael addition with the oxidized polyphenol; or (ii) Both the first polymer and the second polymer contain multiple amino groups for Michael addition with the oxidized polyphenol but they are not the same; or (iii) Both the first polymer and the second polymer contain multiple hydroxyl groups and multiple amino groups simultaneously for Michael addition with the oxidized polyphenol but they are not the same. When both the first polymer and the second polymer possess amino groups, after Michael addition with the oxidized polyphenol, a polymeric network is formed from two different polymers crosslinked by both chemical interactions (i.e. covalent bonds) and physical interactions (i.e. hydrogen bonds, van der Waals forces, electrostatic interaction, TT-TT stacking, metal-ligand coordination, and polymer chainentanglement). When only one of the first polymer and the second polymer possesses amino groups, after Michael addition with the oxidized polyphenol, a polymeric network is formed from the covalently crosslinked multiple amino groups containing polymer, while the other polymer, without amino groups, physically interacts with the polymeric network through hydrogen bonding, electrostatic interaction, and polymer chain entanglement. (D) A metallic compound including aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), zinc(II), etc. (E) A solvent system including water and alcohol; The binder composition prepared according to the method described herein is bio-based, pale in color, and odorless; A substrate for coating with the binder composition, comprising cellulose, keratin, fibroin, mineral, cotton, wool, silk, acetate, acrylic, aramid, olefin, polyester, rayon, spandex, polyethylene terephthalate (PET), nylon, polyurethane (PU), polypropylene (PP), rubber, leather, wood, glass, metal, ceramics, plastics, etc.

[0034] In an embodiment, said composition comprises: 0.01 to 60 wt% of the polyphenol compound; 0.5 to 90 wt% of the first polymer; 0.5 to 90 wt% of the second polymer; 0.01 to 50 wt% of the metallic compound; 1 to 99 wt% of the solvent system; The wt% based on the total weight of the composition.

[0035] In an embodiment, said composition is prepared by dissolving all components in the solvent system at temperature of 15 °C to 95 °C with air bubbling to provide oxygen for oxidation of polyphenol and mixing for 1-5 hour.

[0036] In an embodiment, the pH value of said composition is adjusted to and maintained at pH 7 to pH 10 favorable for Michael addition. Aqueous sodium hydroxide solution at concentration around 1 M is used for pH adjustment. The mixture is further air-bubbled and mixed at temperature of 15 °C to 95 °C for 1-5 hours

[0037] In an embodiment, said composition is cooled by standing at room temperature. pH value of the composition is adjusted to neutral by addition of aqueous hydrochloric acid at concentration around 1 M.

[0038] This invention provides a binder used as adhesive, coating, or laminate. In an embodiment, said binder comprises said binder composition. For immediate use, said binder composition is allowed to cool down to around 15 °C to 30 °C by standing at room temperature, then it is applied onto mechanical, chemical, or energetic pretreated substrate surface using a coating machine. The bonded, or coated, or laminated substrate is cured at temperature of 30 °C to 90 °C for at least 10 minutes. For storage, said binder composition is transferred into a container. It is allowed to stand at room temperature before the container is sealed.

[0039] This invention also provides a pigment paste comprising said binder composition, pigment particles, thickeners, sequestering agents, surfactants, humectants, defoamers, and hand modifiers; Weight % of each pigment paste component depends on the formulation; The mixture of pigment paste components are thoroughly mixed to prepare the pigment paste for pigment printing; For immediate use, the prepared pigment paste is loaded to a printing machine. After printing the substrate, the paste is dried, and undergoes fixation at temperature below 100 °C; For storage, the prepared pigment paste is transferred into a container. It is allowed to stand at room temperature before the container is sealed.

[0040] Binder composition component (A) a polyphenol

[0041] In an embodiment, the binder composition component (A) is a polyphenol originated from natural resources.

[0042] As used herein, the term “polyphenol” refers to an organic molecule with multiple phenol structures. Polyphenols are extracted from natural resources such as plant tissues including leaf, bark, flowers and fruits. Polyphenols comprise multiple phenol units with a high content of dihydroxyphenyl (catechol) and trihydroxyphenyl (gallic acid). They are classified into flavonoids, stilbenes, lignans, and phenolic acids based on the units’ number and binding structure. Tannic acid is one of the polyphenols, and it has a chemical formula of C76H52O46, a decagalloyl (i.e. ten galloyl moieties per molecule), a central glucose core with five digalloyl ester groups covalently attached to the center. There are multiple source of hydrogen donor (hydrogen in amine and hydroxyl group) and acceptor (O in carbonyl and N in amine group). Also, tannic acid has ten aromatic benzene units for TT-TT stacking and hydrophobic interactions. Tannic acid is a weak acid (pKa around 6) due to the numerous phenol groups in the structure. In a solvent with a pH higher than pKa, tannic acid is a polyanion (i.e. negatively charged), and it can bind to other materials by electrostatic interactions. Lone pair electrons of tannic acid phenolic hydroxyl groups form coordination bonds with metal ions such as Al3+, Ca2+, Cu2+, Au3+, Ag+, Ti4+, Zn2+, etc. In the presence of oxygen or oxidizing agents, phenolic hydroxyl groups of tannic acid are oxidized to quinone which can react with amino groups of polymers such as chitosan and gelatin to form covalent bonds by Michael addition provided that pH of the solution is adjusted to pH 7 to pH 10.

[0043] Binder composition component (B) a first bio-based polymer

[0044] In an embodiment, the binder composition component (B) is a first bio-based polymer selected from multiple amino groups containing polymers, or multiple hydroxyl groupscontaining polymer, or multiple amino groups and multiple hydroxyl groups containing polymer.

[0045] As used herein, the term “multiple amino groups containing polymer” refers to a polymeric molecule having many amino groups along the entire hydrocarbon chain. The term “multiple hydroxyl groups containing polymer” refers to a polymeric molecule having many hydroxyl groups along the entire hydrocarbon chain, for example, poly(vinyl alcohol) made from sugar cane and alcohol. The term “multiple amino groups and multiple hydroxyl groups containing polymer” refers to a polymeric molecule having many amino groups and many hydroxyl groups along the entire hydrocarbon chain simultaneously, for example, chitosan and gelatin. Amino groups of polymer can covalently bond with quinone moieties of oxidized tannic acid by Michael addition at pH 7 to 10.

[0046] Binder composition component (C) a second bio-based polymer

[0047] In an embodiment, the binder composition component (C) is a second bio-based polymer selected from multiple amino groups containing polymers, or multiple hydroxyl groups containing polymer, or multiple amino groups and multiple hydroxyl groups containing polymer.

[0048] As used herein, the term “multiple amino groups containing polymer” refers to a polymeric molecule having many amino groups along the entire hydrocarbon chain. The term “multiple hydroxyl groups containing polymer” refers to a polymeric molecule having many hydroxyl groups along the entire hydrocarbon chain, for example, poly(vinyl alcohol) made from sugar cane and alcohol. The term “multiple amino groups and multiple hydroxyl groups containing polymer” refers to a polymeric molecule having many amino groups and many hydroxyl groups along the entire hydrocarbon chain simultaneously, for example, chitosan and gelatin. Amino groups of polymer can covalently bond with quinone moieties of oxidized tannic acid by Michael addition at pH 7 to 10.

[0049] In order to undergo Michael addition between tannic acid and polymer, the selection criteria of a first polymer and a second polymer are listed below: (i) at least the first polymer or the second polymer contains multiple amino groups for Michael addition with the oxidized polyphenol; or (ii) both the first polymer and the second polymer contain multiple amino groups for Michael addition with the oxidized polyphenol but they are not the same; or (iii) both the first polymer and the second polymer contain multiple hydroxyl groups and multiple amino groups simultaneously for Michael addition with the oxidized polyphenol but they are not the same.

[0050] The incorporation of two different polymers may have synergistic effects on mechanical properties of the resulting binder, e.g. enhanced bonding strength and toughness.

[0051] Binder composition component (D) a metallic compound

[0052] In an embodiment, the binder composition component (D) is a metallic compound selected from periodic table except arsenic, beryllium, cadmium, hexavalent chromium, lead, and mercury (note: these are classified as toxic metals in webpage of the Occupational Safety and Health Administration, U.S. Department of Labor).

[0053] A metal ion is released after dissolving the metallic compound in an aqueous solvent. A coordination complex is formed with a central metal ion and a surrounding array of ligands. Phenolic hydroxyl groups of tannic acid provide lone pair electrons to bind with metal ions such as aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), zinc(II), etc.

[0054] Binder composition component (E) a solvent system

[0055] In an embodiment, the binder composition component (E) is a solvent system including protic solvents such as water and alcohol.

[0056] The other binder composition components (A) to (D) are soluble in water and alcohol because components (A) to (C) have hydrophilic functional groups such as hydroxyl, amine, and component (D) is ionic in nature.

[0057] Substrate

[0058] In an embodiment, the substrate for coating with the binder composition, comprising cellulose, keratin, fibroin, mineral, cotton, wool, silk, acetate, acrylic, aramid, olefin, polyester, rayon, spandex, polyethylene terephthalate (PET), nylon, polyurethane (PU), polypropylene (PP), rubber, leather, wood, glass, metal, ceramics, plastics, etc.

[0059] Binder layer

[0060] In an embodiment, the binder layer is formed from the present invention binder composition as described herein, which comprises at least (A) a polyphenol, and (B) a first biobased polymer selected from i) a multiple amino groups containing polymer, or ii) a multiple hydroxyl groups containing polymer, or iii) a multiple amino groups and multiple hydroxyl groups containing polymer, and (C) a second bio-based polymer selected from i) a multiple amino groups containing polymer, or ii) a multiple hydroxyl groups containing polymer, or iii) a multiple amino groups and multiple hydroxyl groups containing polymer, provided that at least the first polymer or the second polymer contains multiple amino groups for Michael addition with the oxidized polyphenol, and the first polymer and the second polymer are not the same, and (D) a metallic compound except arsenic, beryllium, cadmium, hexavalent chromium, lead, and mercury compounds, and (E) a solvent system selected from proticsolvents including water and alcohol. The binder composition was prepared as described in the present invention including oxidation and Michael addition.

[0061] Article

[0062] In an embodiment, the invention provides an article comprising at least one component formed from the coated substrate according to any embodiment disclosed herein.

[0063] In an embodiment, the article is a laminate.

[0064] Nonlimiting examples of articles include i) apparel, accessories such as handbags and belts, and ii) upholstery such as home, office, and automotive interior parts, and iii) home furnishings such as table covers, draperies, show curtains, and iv) tarpaulins, covers, industrial blankets such as chemical treated fabric or textile for industrial or civil engineering applications, and v) pressure-sensitive applications such as shoe construction tapes, wall-board sealing tapes.

[0065] In an embodiment, the article is a pigment printed product.

[0066] Nonlimiting examples of articles include i) a fabric with pigment print, and ii) a paper with pigment print, and iii) a metal object with pigment print, and iv) a glass object with pigment print, and v) a ceramic object with pigment print.

[0067] The following non-limiting examples are provided to illustrate the present invention and in no way limit the scope thereof.

[0068] Example 1. Tannic acid / poly( vinyl alcoholj / gelatin / AlCh; cotton fabric / cotton fabric

[0069] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and aluminum chloride hexahydrate (0.3 g) were added to water (16 m ) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM D1876. Results were compared with commercial binders, and data were shown on Table 1.

[0070] Example 2. Poly(vinyl alcoholj / gelatin / AlCh; cotton fabric / cotton fabric (Control)

[0071] Poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and aluminum chloride hexahydrate (0.3 g) were added to water (16 mb) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuringpH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on apiece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0072] Example 3. Tannic acid / poly( vinyl alcohol ) / gelatin; cotton fabric / cotton fabric (Control)

[0073] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), and gelatin (0.8 g) were added to water (16 m ) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0074] Example 4. Poly (vinyl alcohol) / gelatin; cotton fabric / cotton fabric (Control)

[0075] Poly(vinyl alcohol) (3.5 g), and gelatin (0.8 g) were added to water (16 mb) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0076] The inventive binder compositions in Examples 2, 3, and 4 are control of the inventive binder composition in Example 1. The T-peel strength results indicate that the T-peel strengthof mixture of PVA and gelatin is around 550 N / m. The addition of tannic acid to the PVA:gelatin composite causes a 120 N / m increase in T-peel strength. The addition of aluminum chloride to the PVA:gelatin composite causes an increase of 430 N / m in T-peel strength. The addition of tannic acid and aluminum chloride to the PVA:gelatin composite increases the T-peel strength by around 670 N / m.

[0077] Example 5. Tannic acid / poly(vinyl alcohol) / gelatin:KCl; cotton fabric / cotton fabric (Control)

[0078] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and potassium chloride (0.3 g) were added to water (16 m ) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 oC with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown in Table 1. Potassium ion has a lower charge density as compared to the metallic compounds selected by this invention, and it leads to relatively weak coordination bond between potassium ion and polymer or crosslinker and the contribution of metal-ligand coordination for potassium is not observed from the peeling strength results.

[0079] Example 6. Tannic acid / poly(vinyl alcoholj / gelatimCaCh; cotton fabric / cotton fabric

[0080] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and calcium chloride (0.3 g) were added to water (16 mb) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 oC with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of cotton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the cotton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated cotton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0081] Example 7. Tannic acid / poly(vinyl alcohol) / gelatin:ZnC12; coton fabric / coton fabric

[0082] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and zinc chloride (0.3 g) were added to water (16 m ) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of coton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the coton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated coton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0083] Example 8. Tannic acid / poly( vinyl alcohol) / gelatin:NaCl; coton fabric / coton fabric

[0084] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and sodium chloride (0.3 g) were added to water (16 mb) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of coton fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the coton fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peel strength of the laminated coton fabric assembly was measured according to test standard ASTM DI 876. Results were compared with commercial binders, and data were shown on Table 1.

[0085] Example 9. Tannic acid / poly(vinyl alcoholj / gclatin: AICIv nylon fabric / nylon fabric

[0086] Tannic acid (0.04 g), poly(vinyl alcohol) (3.5 g), gelatin (0.8 g), and aluminum chloride hexahydrate (0.3 g) were added to water (16 mb) and then adjusted to pH 8.5 with 1 M sodium hydroxide solution. The reaction mixture was heated to 80 °C with stirring and air bubbling for 60 minutes ensuring pH 8.5 was maintained. After 1 hour, the reaction mixture was cooled to ambient temperature, and the pH was adjusted to neutral with 1 M hydrochloric acid solution. The final solution was then applied on a piece of nylon fabric (woven, plain construction, weight: 134 g / m2, thickness: -0.34 mm). Another piece of the nylon fabric was covered on top of the binder composition coated fabric. The assembly was pressed to give a binder layer of thickness within 0.025 mm. Then the assembly was cured at 60 °C for 40 minutes. T-peelstrength of the laminated cotton fabric assembly was measured according to test standard ASTM D1876. Results were compared with commercial binders, and data were shown on Table 1.Table 1: Comparison of T-peel strength between inventive binder compositions and commercial binders

[0087] Effect of accelerated aging on T-peel strength

[0088] Another set of test specimens of Example 1 (tannic acid / PVA / gelatin / AlCh; cotton fabric / cotton fabric) underwent an accelerated aging at 57 °C, 95% RH, for 48 hours before the ASTM DI 876 T-peel strength test. The test results were shown on Table 2. Using independent samples t test to compare the two sets of data, the p-value of equality of variances was printed as 0.803 (p > 0.001), and it indicated that the variance in T-peel strength of after aging sample is not significantly different from that of sample under standard condition.Table 2: ASTM D1876 T-peel strength of tannic acid / PVA / gelatin / AlCh bonded cotton fabric / cotton fabric with and without accelerated aging

Claims

What is claimed is:

1. A bio-based binder composition, comprising : a. 0.01 to 60 wt.% of a polyphenol; b. 0.5 to 90 wt.% of a first bio-based polymer, comprising multiple amino or hydroxyl groups as first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; c. 0.5 to 90 wt.% of a second bio-based polymer; d. 0.01 to 50 wt.% of a metallic compound, said metallic compound is selected from the group consisting of aluminum(III), calcium(II), copper(II), gold(III), silver(I), titanium(IV), sodium (I) and zinc(II) compounds; and e. 1 to 99 wt.% of a protic solvent; wherein said bio-based binder composition can be adjusted to a condition for forming a transparent polymeric network cross-linked by covalent and non-covalent interactions.

2. The bio-based binder composition of claim 1, wherein said first Michael donors comprises both amino groups and hydroxyl groups.

3. The bio-based binder composition of claim 2, wherein said second bio-based polymer comprises multiple amino or hydroxyl groups as second Michael donors for a second Michael addition reaction with a second Michael acceptor formed by oxidation of said polyphenol.

4. The bio-based binder composition of claim 3, wherein said second Michael donors are amino groups or hydroxyl groups different from said first Michael donors.

5. The bio-based binder composition of claim 1, wherein: a. said polyphenol comprises one or more of tannic acid, tannins, phenolic acids, flavonoids, lignin, lignans, or stilbenes; b. said first bio-based polymer or second bio-based polymer comprises one or more of cellulose, poly(vinyl alcohol), chitosan, or gelatin; or c. said protic solvent comprises water or alcohol.

6. The bio-based binder composition of claim 1, wherein said condition comprises dissolving said bio-based binder composition at a temperature at 15 to 95°C while oxidizing said polyphenol.

7. The bio-based binder composition of claim 6, wherein said condition further comprises adjusting and maintaining at a suitable pH for said first or second Michael addition reaction.

8. The bio-based binder composition of claim 7, wherein said condition further comprises adjusting pH to neutral and cooling to room temperature.

9. The bio-based binder composition of claim 1, wherein said bio-based binder composition is a composition selected from the group consisting of: i. tannic acid, poly(vinyl alcohol), gelatin, aluminum chloride hexahydrate and water; ii. tannic acid, poly(vinyl alcohol), gelatin, calcium chloride and water; iii. tannic acid, poly(vinyl alcohol), gelatin, zinc chloride and water; and iv. tannic acid, poly(vinyl alcohol), gelatin, sodium chloride and water.

10. An article comprising a substrate coated with the bio-based binder composition of claim 1.

11. The article of claim 10, wherein said substrate comprises synthetic or natural materials.

12. A method of preparing a bio-based binder, comprising the steps of: a. Providing a bio-based binder composition comprising: i. 0.01 to 60 wt.% of a polyphenol; ii. 0.5 to 90 wt.% of a first bio-based polymer, comprising multiple first Michael donors for a first Michael addition reaction with a first Michael acceptor formed by oxidation of said polyphenol; iii. 0.5 to 90 wt.% of a second bio-based polymer; iv. 0.01 to 50 wt.% of a metallic compound; and v. 1 to 99 wt.% of a protic solvent; b. Dissolving said bio-based binder composition at 15 to 95°C and oxidizing said polyphenol to form a first solution; c. Adjusting said first solution to a pH value favorable for said first Michael addition reaction to form a second solution; and d. Adjusting said second solution to a suitable pH value to form said bio-based binder.

13. The method of claim 12, wherein said second bio-based polymer comprises multiple second Michael donors for a second Michael addition reaction with a second Michael acceptor formed by oxidation of said polyphenol and said step (c) further comprises adjusting said first solution to a pH value favorable for said second Michael addition reaction to form said second solution.

14. The method of claim 12, wherein said bio-based binder composition is a composition selected from the group consisting of: i. tannic acid, poly(vinyl alcohol), gelatin, aluminum chloride hexahydrate and water; ii. tannic acid, poly(vinyl alcohol), gelatin, calcium chloride and water; iii. tannic acid, poly(vinyl alcohol), gelatin, zinc chloride and water; and iv. tannic acid, poly(vinyl alcohol), gelatin, sodium chloride and water.

15. The method of claim 12, further comprises one or more of the following steps: a. said temperature of step (b) is 80 to 90°C;b. said oxidizing at step (b) comprises air bubbling of said first solution; c. said pH value of step (c) is pH 7 to 10; d. said step (c) comprises further oxidizing said polyphenol; and e. said suitable pH value of step (d) is neutral.

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