MXPA06008248A - Formaldehyde-free adhesives and lignocellulosic composites made from the adhesives - Google Patents

Abstract

A first variant of an adhesive composition for making a lignocellulosic composite includes soy protein and/or lignin;at least one substantially formaldehyde-free curingagent that includes at least one amine, amide, imine, imide, or nitrogen-containing heterocyclic functional group that can react with at least one functional group of the soy protein;and at least one compound selected from a boron compound, a group IA oxide or hydroxide, or a group IIA oxide or hydroxide. A second variant of an adhesive composition includes a first component selected from soy protein and/or lignin;and at least one substantially formaldehyde-free curing agent selected from a reaction product of epichlorohydrin with ethylenediamine, a reaction product of epichlorohydrin with bis-hexamethylenetriamine, or a reaction product of epichlorohydrin with hexamethylenediamine.

Description

FORMALDEHYDE-FREE ADHESIVES AND LIGNOCELLULOSE COMPOUNDS MADE FROM ADHESIVES Field of the Invention The present invention relates to adhesives for making lignocellulosic compounds.

Background Compounds based on lignocellulosic compounds are formed from pieces of small dimensions of cellulosic material that are adhered with an adhesive (i.e., a bond). In general, a solid wood is broken into smaller pieces such as strands, fibers and chips. An adhesive composition is then added to the wood component. The resulting mixture is subjected to the heat and the resulting pressure in a compound. The adhesive mixture is generally the only non lignocellulosic component. The most commonly used wood adhesives are phenol-for-aldehyde (PF) resins and urea-for-aldehyde (UF) resins. There are at least two concerns with the PF and UF resins. First, volatile organic compounds (VOCs) are generated during the manufacture and use of compounds based on lignocellulosic A growing concern about the effect of emissive VOCs, especially formaldehyde, on human health has driven a need for more environmentally acceptable adhesives. Second, PF and UF resins are made from petroleum products. Oil reserves are naturally limited. The wood composite industry would benefit greatly from the development of formaldehyde-free adhesives made from renewable natural sources.

Soy protein was used as a wood adhesive for the production of plywood from the 1930s to the 1960s. Oil-based adhesives replaced soy adhesives due to relatively low adhesion strength and strength. to the water of soy protein adhesives. However, soy protein is a non-expensive, abundant, renewable material that is environmentally acceptable.

Extract of the Invention Adhesive compositions and methods for making lignocellulosic compounds are disclosed in the present invention.

A first variant of the adhesive compositions includes soy protein and / or lignin; at least one curing agent substantially free of formaldehyde including at least one amine, amide, imine, imide, or nitrogen-containing heterocyclic functional group that can react with at least one functional group of the soy protein; and at least one compound that is selected from a boron compound, an oxide or hydroxide of group IA, or an oxide or hydroxide of group IIA.

A second variant of the adhesive composition includes a first component that is selected from soy protein and / or lignin; and at least one curing agent substantially free of formaldehyde which is selected from a product of the reaction of epichlorohydrin with ethylene diamine, a product of the reaction of epichlorohydrin with bis-hexamethylenetriamine, or a product of the reaction of epichlorohydrin with hexamethylenediamine.

Also included in the present invention are methods for making a lignocellulosic compound that includes applying the first variant or the second variant of the adhesive composition described above to at least one lignocellulosic substrate, and adhering the lignocellulosic substrate with the applied adhesive, to at least one other lignocellulosic substrate.

The lignocellulosic compounds manufactured according to these methods are also described herein.

Brief Description of the Figures Certain embodiments will be described in more detail with reference to the following figures: Figure 1 is a graph representing the dry-cut resistance of several examples of the adhesive compositions described herein.

Figure 2 is a graph representing the shear strength of several other examples of adhesive compositions disclosed herein.

Figure 3 is a graph representing the cut resistance of several other examples of adhesive compositions disclosed herein.

Detailed Description of Various Embodiments To facilitate understanding, the following term used here is described below in more detail: "Lignin" refers in general to a group of phenolic polymers that confer resistance and rigidity to the plant material. Lignins are very complex polymers with many couplings, and therefore tend to be referred to in more generic terms. The lignins may include, for example, analytical lignin preparations such as Brauns lignin, cellulolytic enzyme lignin, dioxan acidolysis lignin, ground wood lignin, Klason lignin, and periodate lignin, and industrial lignin preparations such as lignin kraft and lignosulfonates.

The description of the foregoing term is provided solely to assist the reader, and should not be construed as having a lesser scope than that which is understood by one skilled in the art or which limits the scope of the appended claims.

The adhesive composition can be made by reacting or mixing a soy protein and / or a lignin with at least one curing agent substantially free of formaldehyde. A mixture of soy protein and lignin can be used. The substantially formaldehyde-free compound can provide both cure for the adhesive composition and adhesion to the lignocellulosic substrate. In other words, the compound substantially Formaldehyde-free is a difunctional adhesion promoter in the sense that a compound can provide dual functions.

In the first variant described above, the adhesive also includes at least one boron compound, an oxide or hydroxide of group IA, or an oxide or hydroxide of group IIA. In the second variant described above, the curing agent is specifically a product of the reaction of epichlorohydrin with ethylene diamine, a product of the reaction of epichlorohydrin with bis-hexamethylenetriamine, a product of the reaction of epichlorohydrin with hexamethylenediamine, or a mixture from them. Both the first and the second variant of the adhesive composition can be provided as a two-part system in which the protein or lignin comprises a part or package and the curing agent comprises the second part or package. In both the first and the second variant, all parts or components of the composition can be in the form of aqueous solutions or dispersions. Therefore, volatile organic solvents can be avoided as carrier fluids. These two variants are described in more detail below. Soy protein is an example of protein for use in the adhesives that are currently described. Soybeans contain 38% by weight of protein and the remaining portion comprises carbohydrates, oils and moisture. Soybeans they are processed to increase the amount of soy protein in the processed product. The soy protein products of any form can be used in the disclosed adhesive compositions. The three most common products of soy protein are soybean meal, concentrated soy protein and soy protein isolate (SPI). One of the differences between these products is the amount of soy protein. Soybean meal generally includes approximately 50% by weight of protein, concentrated soy protein includes at least 65% by weight of protein (dry weight), SPI includes at least 85% by weight of protein (dry weight) ). According to certain embodiments of the adhesive composition, the soy protein is SPI or soybean meal.

As mentioned above, lignin may comprise an industrial lignin preparation such as kraft lignin. Generally kraft lignin has limited commercial utility, although tons of waste kraft lignin are produced each year as a byproduct of commercial paper production. In particular, kraft lignin is generally produced from a wood material in the reaction with NaOH and Na2S.

The soy protein or lignin can be prepared for use in the adhesive compositions in any way. Generally, the Soy protein or lignin is included in a carrier or supply liquid such as water or a similar solvent. In particular, the soy protein or lignin can be dissolved in water and the resulting aqueous solution mixed with the curing agent and / or the boron compound. The aqueous adhesive solution can be prepared, for example, by initially mixing the soy protein or lignin in water and adjusting the pH of the mixture to the desired range. When the soy protein or lignin is mixed with a difunctional curing agent, the pH of the soy protein or lignin part may be sufficiently alkaline such that the resulting mixture of protein and difunctional curing agent is non-acidic, or more preferably alkaline. For example, the pH of the portion of soy protein or lignin can be from 7 to 14 deriving at a pH greater than 6 to 11 for the two-part mixture combined. The pH can be adjusted by adding basic substances such as, for example, alkali metal hydroxides, ammonium hydroxide, amines or pyridine. The amount of soy protein or lignin dissolved in the water can be adjusted to provide the desired solids content for the soy or lignin protein part of the two-part system. The solids content of soy protein or lignin can be, for example, from 10% to 70% by weight. The soy protein or lignin solution can be dried by freezing at this stage of the formulation or it can be maintained as a liquid solution. Yes The soy protein or lignin solution is freeze-dried, simply water (or the appropriate carrier fluid) is added to the substance that is freeze-dried before use. Freeze drying reduces the transport costs of the adhesive. The curing agent and / or the boron compound can be mixed with the soy protein or lignin solution to form the final adhesive composition that is applied to the lignocellulosic substrate.

Although not bound to any theory, as mentioned above, it is believed that the molecular structure of the difunctional curing agent includes (1) a reactive site that can cure the adhesive composition and (2) a reactive site that provides adhesion to the lignocellulosic substrate . The reactive cure site and the adhesion reagent site may be located in the same site on the difunctional curing agent. In other words, a first portion of the reactive sites available on a molecule of the difunctional curing agent may react with other molecules of the difunctional curing agent or react with the functional groups (especially carboxylic and amino acids) of the protein. A second portion of the reactive sites in a molecule of the difunctional curing agent can form covalent and / or hydrogen bonds with the lignocellulosic substrate.

Examples of suitable difunctional curing agents include products of the reaction of epoxides with polyamine resins, polyamidoamine resins, or polyamide resins. These resins are generally made from glycidyl ether condensates or polyalkylene polyamines epichlorohydrin and are used as wet strength agents for paper. The resins can be water soluble or water dispersible. These resins generally include a nitrogen-containing heterocyclic functional group that is the reactive site for covalently linking to protein functional groups, covalently linking to nitrogen-containing heterocyclic functional groups of other resin molecules, and covalently linking to carboxylic acid groups and / or hydroxyl in the lignocellulosic substrate.

Commercially available examples of products of the reaction of epoxides with polyamine resins, polyamidoamine resins, or polyamide resins include Kymene® resins available from Hercules Inc. and Arares® resins available from Georgia-Pacific Corporation. Kymene® 557H resins are a specific example that are based on the reaction product of poly (adipic acid with diethylenetriamine) and epichlorohydrin. It is believed that Kymene® 557H resins have a structure that includes a Nitrogen-containing 4-membered ring functional group shown below: An excess of epichlorohydrin is used to control the crosslinking rate during the manufacturing process and to aid in storage stability. Those compositions and processes for their manufacture are disclosed, for example, in U.S. Patent No. 2,926,116 and U.S. Patent No. 2,926,154. Another example of class of polyamine-epichlorohydrin resins are those produced by the reaction of an epihalohydrin, such as epichlorohydrin, with a polyalkylene polyamine, such as ethylene diamine, bis-hexamethylenetriamine and hexamethylenediamine. These polyalkylene polyamine-epihalohydrin resins are described, for example, in U.S. Published Patent Application 20030070783, in U.S. Patent No. 3,655,506, U.S. Patent No. 3,248,353, and U.S. Patent No. 2,595. 935 Kymene® 736 resin is a commercially available example of that polyalkylene polyamine-epichlorohydrin resin.

As mentioned above, at least one boron compound, an oxide or hydroxide of group IA, or an oxide or hydroxide of group IIA can be included in the adhesive composition. The boron compound can be any compound or material that includes at least one boron atom or species. "Group IA" and "group IIA" refer to the classifications of the elements of the Periodic Table of the Elements. Although we are not tied to any theory, we believe that the boron species can potentially chelate with four hydroxyl groups, then serving as a crosslinking agent for the soy protein or lignin. The species of group IA or group IIA can potentially be chelated with a plurality of carboxylic acid groups, then serving as a crosslinking agent for soy or lignin protein.

In particular examples of the boron compound can be boric acid, a boron salt, or a borate ester. As understood by those skilled in the art, boric acid, borate salts and borate esters can be produced from numerous other boron compounds, including but not limited to, metaborates, acyl borates, anhydrous borates, borax, hydrides of boron, and the like. Specific examples of borate salts or borate esters include sodium borate, sodium borate anhydrous, sodium tetraborate, sodium boroformate and sodium borohydride, similarly, one skilled in the art will recognize that boron compounds can be provided as various salts and in various hydration states, including but not limited to, KB5-H20, Na2B07 • 10H2O, Na2B407- 5H20, Mg3B70? 3Cl, K3B306, CaB204 and the like.

In particular, examples of the oxide or hydroxide of group IA or of the oxide or hydroxide of group IIA can be a calcium, sodium or potassium hydroxide or oxide. Examples of compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, or calcium oxide.

The relative amount of soy protein or lignin mixed with the curing agent may vary according to, for example, the number of reactive sites available and the molecular weight of the curing agent. For example, the mixing ratio of the soy or lignin protein to the curing agent may be in the range of 1: 1 to 1000: 1, more particularly 1: 1 to 100: 1, based on the dry weight. In a particular embodiment, the mixing ratio of the soy protein or lignin to the curing agent is from 2: 1 to 30: 1, based on the dry weight. In other words, the adhesive composition can include from 0.1% to 50%, more particularly from 0.5% to 10% by weight of the curing agent, based on the dry weight combination of soy or lignin protein and the curing agent. The amount of the boron compound, of the group IA oxide or hydroxide, of the group IIA oxide or hydroxide added to the mixture may also vary. For example, it may be included from 0.1% to 20%, more particularly from 0.5% to 10% by weight of the compound (s), in the adhesive based on the combined dry weight of the soy protein, the compound and the curing agent.

The adhesive composition may also include additives and fillers that are found in lignocellulosic adhesives such as bactericides, insecticides, silica, wax, wheat flour, tree bark meal, nut shell meal and the like.

The ingredients of the adhesive composition can be mixed together in any order and at standard temperature and pressure (i.e., at 25 ° C and at 1 atmosphere). Generally, the ingredients are soluble in water or dispersible in water. The solids content of the resulting final adhesive mixture can be 15% to 70%, more particularly 20% to 68% by weight. Each (only one) part of the adhesive system can be provided to the end user in the form of a concentrate that dilutes the end user in the mixing ratios and the appropriate solids contents.

According to one approach, the adhesive composition can be used as a two part system in which the soy protein or lignin component comprises one part and the curing agent comprises the second part. The two parts are mixed together briefly before using them. The composition can have an open time of up to 5 days. As used herein, "open time" indicates the time from the mixing of the two parts to the time at which the mixed composition is cured to a point where it is no longer workable. In another approach, all the ingredients of the adhesive composition are premixed together in a one part system which is then supplied to an end user. In the one-part system the adhesive composition can be applied to a substrate without the need to mix the two different components together.

The adhesive compositions are heat-curable. In other words, the heating of the two-part mixture forms covalent bonds between the individual molecules of the adhesive composition and covalent and / or hydrogen bonds between the molecules of the adhesive mixture and the lignocellulosic particles. That curing generally occurs during the thermal pressing step of the compound formation. Therefore, the curing temperature of the adhesive composition is adapted to match the heating temperatures used in the formation of the compound. These curing temperatures can be in the range, for example, from 90 ° C to 200 ° C, more particularly from 1100 ° C to 160 ° C.

The lignocellulosic compounds that can be produced with the adhesives described herein include particle board, plywood, oriented strand panel (OSB), sheet metal panel, fiber board (including medium and high density fiberboard), stripped wood Parallel (PSL), laminated strand lumber (LSL), laminated veneer lumber (LVL), and similar products. In general, these compounds are first made by mixing ground lignocellulosic materials with an adhesive that serves as a bond that adheres the ground lignocellulosic materials in a unitary densified mass. Examples of suitable lignocellulosic materials include wood, straw (including rice, wheat and barley), flax, hemp and bagasse. The ground lignocellulosic materials can be processed in any suitable substrate form and size, such as blades, flakes, fibers, strands, sheets, cuttings, shavings, sawdust, straw, stems, chips and mixtures thereof.

The lignocellulosic materials are mixed together with the adhesive composition that serves as a bond, and are formed in a desired configuration to provide a pre-bonded assembly.

The preadhermed assembly is then subjected to high heat and pressure to provide the lignocellulosic composite product. For example, the pre-bonded assembly can be subjected to temperatures of 120 ° C to 225 ° C in the presence of varying amounts of vapor, generated by the release of moisture transported from lignocellulosic materials.

The amount of adhesive mixed with the lignocellulosic particles may vary according to, for example,, the type of compound desired, the type and amount of the lignocellulosic material and the specific adhesive composition. In general, it is possible to mix from 1% to 12%, more particularly from 3% to 10%, by weight of adhesive with the lignocellulosic material, based on the total combined weight of the adhesive and lignocellulosic material. The mixed adhesive composition can be added to the ground lignocellulosic particles by spraying or similar techniques while the lignocellulosic particles are tumbled or agitated in a similar mixer or mixer. For example, a stream of ground lignocellulosic particles can be mixed with a stream of the mixed adhesive composition and then subjected to mechanical agitation. Adhesive compositions can also be used to produce plywood or laminated veneer lumber (LVL). The adhesive composition can be applied on surfaces of coating by roller coating, knife coating, curtain coating, or spraying. Then a plurality of coatings are placed to form sheets of the required thickness. The matrices or sheets are then placed in a heated press (eg, a platen) and compressed to effect the consolidation and curing of the materials in a panel. The fiberboard can be made by the wet felting / wet pressing method, the dry felting / dry pressing method, or the wet felting / dry pressing method.

The presently disclosed adhesives provide a tough adhesion between the lignocellulosic substrates. The adhesives also provide structural compounds with surprisingly high mechanical strength. In addition, the adhesive compositions are substantially free of formaldehyde (which includes any compound that can degenerate to form formaldehyde). For example, the adhesive compositions do not contain any formaldehyde (and compounds that generate formaldehyde) that is detectable by conventional methods or, alternatively, the amount of formaldehyde (and compounds that generate formaldehyde) is negligible from an environmental and site regulatory point of view. of work.

The specific examples described below are for illustrative purposes and should not be considered. which limit the scope of the appended claims.

Example 1 - Preparation of Adhesive Mixture - Method 1 Soybean meal (SF) (30 g dry weight) was slowly added to 170 ml of water in a 600 ml flask with stirring. The pH value of the soy flour suspension was adjusted to 10 with 50% by weight of a NaOH solution. The SF mixture was stirred for 20 minutes and used as a control to adhere maple wood coatings which are described below. 38% by weight of an aqueous solution of Kymene 736 (K736, from Hercules, Inc., Wilmington, DE) (15.8 g) was added to the mixture of alkaline SF. The resulting aqueous mixture of SF-K736 was stirred for 30 minutes and then used as an adhesive for maple wood coatings which are described below in Example 3. The total solids content of the SF-K736 adhesive was 16, 7% and the weight ratio of SF: K736 was 5: 1. The SF-K736 adhesives with different weight ratios of SF: K736 were prepared by adjusting the amount of K736 and water.

Example 2 - Preparation of Adhesive Mixture - Method 2 38% of an aqueous solution of K736 (12.6 g) was added to 45 ml of water with stirring. The soybean meal (48 g dry weight) was added slowly to the K736 solution with vigorous stirring. The resulting SF paste was used as a control to adhere maple wood coatings as described below in Example 3. Other examples of adhesives were made by dissolving 38% by weight of a solution of K736 (12.6 g) and 0.53 g of NaOH or 0.77 g of Na2B407-5H20 in 45.3 ml of water. The SF (48 g dry weight) was added slowly to the K736-NaOH solution or to the K736-Na2B407 solution with vigorous stirring. The resulting SF-K736 adhesives had 50% by weight of total solids content and contained 1% by weight of NaOH or 1% by weight of Na2B407 based on the total solids content. The weight ratio of SF: K736 was 10: 1. The resulting SF: K736 adhesives were used to adhere maple wood coatings as described below in Example 3.

Example 3 - Preparation and Testing of Wood Compounds Mixtures of SF-K736 adhesives prepared as described in Examples 1 and 2 were evaluated for their ability to adhere together two pieces of maple wood veneer. The Adhesive preparation for the test was applied to one side and to the end of a strip of maple wood veneer (1 cm x 10 cm). Two pieces of the maple veneer strips were stacked together and heat-pressed at 120 ° C for 5 minutes. 5 The applied pressure was 11 kg / cm2. The adhesion area for each specimen of two-layer composite was 2.0 cm2. The total spreading rate of the adhesives was 9 mg / cm2 of the adhesion area. The gap cut resistance was measured with an Instron TTBML machine with a crosshead speed of 10 1.0 mm / min using conventional techniques. The maximum shear strength when breaking was recorded.

The specimens of two-layer wood composites bonded with the adhesives were subjected to a soaking test with water and drying (WSAD) and a boiling water test (BWT). For a WSAD test, the specimens were soaked in water at room temperature for 24 hours, dried in a smoke hood at room temperature for 24 hours, and then evaluated for shear strength. A BWT was performed in accordance with the Standard . for United States Voluntary Products PS 1-95 for Tertiary Wood for Construction and Industrial (published by the United States Department of Commerce through the Association of Wood Design, Tacoma, WA). The specimens were boiled in water for 4 hours, dried for 24 hours at 63 ° C ± 3 ° C, boiled in water again for 4 hours and then cooled with tap water. The cut resistance of several specimens was evaluated when they were wet. The cut resistance determined in this way was termed BWT / wet moisture resistance. The cut resistance was also measured after several specimens had dried at room temperature in a smoke hood for 24 hours. This resistance was called BWT / dry strength.

The effect of the weight ratio of SF: K736 on the shear strength of dry wood composites bonded with SF-K736 adhesives is shown in Figure 1. The data shown in Figure 1 are the results with adhesives according to the preceding Example 1. At all weight ratios, a mixture of SF and K736 provided greater cut-off resistance compared to SF alone. The cut resistance increased significantly with the increase in the weight ratio of SF: K736 from 5: 1 to 10: 1. When the weight ratio of SF: K736 increased from 10: 1 to 20: 1, the cut resistance decreased slightly. However, a further increase in the weight ratio resulted in a significant loss of cut resistance.

Compared with a suspension of SF (composition A) at 35% total solids content, a mixture of SF-K736 (composition B) resulted in a higher shear strength (see Figure 2). The addition of 1% by weight of NaOH to the mixture of SF-K736 (composition C) gave rise to an improved cut resistance compared to the SF-T736 adhesive. The replacement of NaOH with Na2B407 (composition D) further increased the shear strength. At 2% by weight, NaOH (composition E) and Na2B07 (composition F) had the same effect on the improvement of the shear strength and had a slightly lower strength than Na2B407 at 1% by weight (see Figure 2).

At 50% of the total solids content, SF-K736 adhesives were sticky, but could easily be applied to coatings. The data shown in Figure 3 further confirms the conclusions drawn from Figures 1 and 2: the SF-K736 adhesives could derive in a much higher dry shear strength than SF alone; the addition of NaOH (composition C) or Na2B407 (composition D) increased the shear strength further; and Na2B407 at 0.67% by weight gave higher shear strengths than 1% by weight NaOH. In addition, the wood compounds that were adhered with SF-K736 adhesives were much more water resistant than SF alone. When the wood compounds that adhered with SF alone or with SF-K736 adhesives were subjected to the boiling water test (BWT), some delamination occurred for wood compounds adhered with SF alone, but no delamination was observed for those adhered with SF-K736 adhesives. SF-K736-NaOH adhesives provided BWT / dry and BWT / wet-cut resistors slightly compared to SF-K736 adhesives and SF-K736-Na2B407 adhesives. The adhesives SF-K736-Na2B407 derived in the highest resistance to the cut (dry, WSAD, BWT / dry and BWT / wet) among all the adhesive formulations. In other words, Na2B40 greatly improved the shear strength and water resistance of the resulting wood composites.

Example 4 - Preparation of Kraft Lignin Adhesive - K736 38% by weight of a solution of K736 (10.5 g) was added to 17.5 ml of water with stirring. Kraft lignin (20 g dry weight) was slowly added to the diluted K736 solution with vigorous stirring. The resultant kraft-K736 lignin adhesive had 50% by weight total solids content and was used to adhere maple wood coatings. The adhesives were applied to one side and to the end of a strip of maple wood siding (1 cm x 10 cm). Two pieces of maple veneer strips were piled together and heat-pressed at 150 ° C for 5 minutes. The applied pressure was 11 kg / cm2. The area of Adhesion for each specimen of two-layer composite was 2.0 cm2. The total spreading rate of the adhesives was 9 mg / cm2 of the adhesion area.

Having illustrated and described the principles of the methods, compositions and compounds disclosed with references to various embodiments, it should be apparent that these methods, compositions and compounds can be modified in the arrangement and in the details without departing from those principles.

Claims (41)

1. An adhesive composition, characterized in that it comprises: soy protein or a mixture of soy protein and lignin; at least one curing agent substantially free of formaldehyde including at least one amine, amide, imine, imide or a nitrogen-containing heterocyclic functional group that can react with at least one functional group of the soy protein; and at least one compound that is selected from a boron compound, an oxide or hydroxide of group IA, or an oxide or hydroxide of group IIA.

2. The composition according to claim 1, characterized in that the composition is substantially free of formaldehyde.

3. The composition according to claim 1, characterized in that the composition includes from 0.5% by weight to 10% by weight of at least one boron compound, an oxide or hydroxide of group IA, or an oxide or hydroxide of group IIA , based on the dry weight of the composition.

4. The composition according to claim 1, characterized in that the boron compound is selected from boric acid, a boron salt or a borate ester.

5. The composition according to claim 1, characterized in that the boron compound comprises sodium borate, sodium borohydride or sodium tetraborate.

6. The composition according to claim 1, characterized in that the curing agent is a product of the reaction of an epoxide with a polyamine resin, a product of the reaction of an epoxide with a polyamidoamine resin, or a product of the reaction of epoxide with a polyamide resin.

7. The composition according to claim 1, characterized in that the curing agent comprises a polyalkylene polyamine-epichlorohydrin resin.

8. The composition according to claim 7, characterized in that the curing agent comprises a product of the reaction of epichlorohydrin with ethylenediamine, bis-hexamethylenetriamine or hexamethylenediamine.

9. The composition according to claim 5, characterized in that the soy protein comprises soybean meal and the curing agent comprises a reaction product of epichlorohydrin and ethylenediamine, bis-hexamethylenetriamine, and examithylene diamine.

10. The composition according to claim 3, characterized in that the composition includes from 2% by weight to 30% by weight of at least one curing agent, based on the dry weight of the composition.

11. The composition according to claim 1, characterized in that the composition comprises a reaction product of the soy protein, at least one curing agent and at least one compound.

12. The composition according to claim 1, characterized in that at least one compound is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.

13. The composition according to claim 8, characterized in that at least one compound is selected from Sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.

14. A method for manufacturing an adhesive composition, characterized in that it comprises mixing together: soy protein or a mixture of soy protein and lignin; at least one curing agent substantially free of formaldehyde including at least one amine, amide, imine, imide, or a heterocyclic functional group containing nitrogen; and at least one compound that is selected from a boron compound, an oxide or hydroxide of group IA or an oxide or hydroxide of group IIA.

15. A method for manufacturing an adhesive composition, characterized in that it comprises: mixing together at least one compound selected from a boron compound, an oxide or hydroxide of group IA or an oxide or hydroxide of group IIA with at least one substantially free curing agent of formaldehyde including at least one amine, amide, imine, imide, or a nitrogen-containing heterocyclic functional group; and contacting the resulting product with soy protein or a mixture of soy protein and lignin.

16. The method according to claim 15, characterized in that at least one compound / curing agent product is contacted with the soybean protein or the soybean and lignin protein mixture under conditions sufficient to react the boron compound product. / curing agent with soy protein.

17. The method according to claim 15, characterized in that the soybean protein comprises soybean meal, at least one curing agent characterized in that it comprises a product of the reaction of epichlorohydrin with ethylenediamine, bis-hexamethylenetriamine or hexamethylenediamine, and at least one The compound is selected from boric acid, a boron salt, a borate ester, sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.

18. An adhesive composition made in accordance with claim 17.

19. An adhesive composition produced from the following ingredients: soy protein or a mixture of soy protein and lignin; at least one curing agent substantially free of formaldehyde including at least one amine, amide, imine, imide or a nitrogen-containing heterocyclic functional group; and at least one compound that is selected from a boron compound, an oxide or hydroxide of group IA or an oxide or hydroxide of group IIA.

20. An adhesive composition, characterized in that it comprises: a first component that is selected from at least one of soy protein, lignin or a mixture thereof; and at least one curing agent substantially free of formaldehyde which is selected from a product of the reaction of epichlorohydrin with ethylene diamine, a product of the reaction of epichlorohydrin with bis-hexamethylenetriamine, or a product of the reaction of epichlorohydrin with hexamethylenediamine.

21. The composition according to claim 20, characterized in that the composition is substantially free of formaldehyde.

22. The composition according to claim 20, characterized in that the composition includes from 2% by weight to 30% by weight of the curing agent, based on the dry weight of the composition.

23. The composition according to claim 20, characterized in that the first component is soy protein.

24. The composition according to claim 23, characterized in that the soy protein comprises soybean meal.

25. The composition according to claim 20, characterized in that the composition comprises a product of the reaction of the first component and at least one curing agent.

26. The composition according to claim 20, characterized in that the first component is lignin.

27. A method for manufacturing an adhesive composition, characterized in that it comprises mixing together: a first ingredient that is selected from soy protein, lignin, or a mixture thereof; and at least one curing agent substantially free of formaldehyde which is selected from a product of the reaction of epichlorohydrin with ethylene diamine, a product of the reaction of epichlorohydrin with bis-hexamethylenetriamine, or a product of the reaction of epichlorohydrin with hexamethylenediamine.

28. An adhesive composition made according to claim 27.

29. A method for manufacturing a lignocellulosic compound, characterized in that it comprises: applying an adhesive composition to at least one lignocellulosic substrate, the adhesive composition comprising (i) soy protein, (ii) at least one curing people substantially free of formaldehyde including at least one amine, amide, imine, imide, or a nitrogen-containing heterocyclic functional group that can react with at least one functional group of the soy protein, and (iii) at least one compound that is selected from a boron compound , an oxide or hydroxide of group IA or an oxide or hydroxide of group IIA; and adhering the lignocellulosic substrate with the adhesive applied to at least one other lignocellulosic substrate.

30. The method according to claim 29, characterized in that the adhesion comprises applying heat and pressure to one set of the lignocellulosic substrate with the applied adhesive and the other lignocellulosic substrate.

31. The method according to claim 29, characterized in that the lignocellulosic substrates comprise ground wood particles and the method comprises: mixing from 1% to 12% by weight of the adhesive composition with a mixture of the ground wood particles, the percentage in Weight is based on the combined weight of the adhesive composition and the ground wood particles; forming the adhesive / wood particle mixture in a predetermined configuration; and apply heat and pressure to the formed mixture.

32. The method according to claim 29, characterized in that the lignocellulosic substrates comprise a wood coating substrate and the method comprises: applying the adhesive composition to at least one surface of the wood coating substrate; form a set of wood cladding substrates with the adhesive applied; and apply heat and pressure to the whole.

33. The method according to claim 29, characterized in that at least one compound is selected from boric acid, a boron salt, a borate ester, sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide, and the Curing agent comprises a product of the reaction of epichlorohydrin with ethylenediamine, bis-hexamethylenetriamine or hexamethylenediamine.

34. A method for manufacturing a lignocellulosic compound, characterized in that it comprises: applying an adhesive composition to at least one lignocellulosic substrate, the adhesive composition comprising (i) a first component that is selected from soy protein, lignin or a mixture thereof and ( ii) at least one curing agent substantially free of formaldehyde which is selected from a product of the reaction of epichlorohydrin with ethylene diamine, a product of the reaction of epichlorohydrin with bis-hexamethylenetriamine, or a product - of the reaction of epichlorohydrin with hexamethylenediamine; and adhering the lignocellulosic substrate with the applied adhesive, to at least one other lignocellulosic substrate.

35. The method according to claim 34, characterized in that the adhesive comprises applying heat and pressure to one set of the lignocellulosic substrate with the applied adhesive and the other lignocellulosic substrate.

36. The method according to claim 34, characterized in that the lignocellulosic substrates comprise ground wood particles and the method comprises: mixing from 1% to 12% by weight of the adhesive composition with a mixture of the ground wood particles, the percentage in Weight is based on the combined weight of the adhesive composition and the ground wood particles; forming the adhesive / wood particle mixture in a predetermined configuration; and apply heat and pressure to the formed mixture.

37. The method according to claim 34, characterized in that the lignocellulosic substrates comprise a wood coating substrate and the method comprises: applying the adhesive composition to at least one surface of the wood coating substrate; form a set of wood cladding substrates with the adhesive applied; and apply heat and pressure to the whole.

38. The method according to claim 34, characterized in that the first component is soy protein.

39. The method according to claim 34, characterized in that the first component is lignin.

40. A lignocellulosic compound made according to the method of claim 29.

41. A lignocellulosic compound made in accordance with the method of claim 34.