RU2575466C2 - Compositions of protein glue with amine-epichlorohydrin and isocyanate additives - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to glue composition, which includes soya, adduct of amine-epichlorohydrin (AE) and isocyanate, where AE adduct includes polyamidoamine-epichlorohydrin polymer (PAE); isocyanate includes poly(hexamethylenediisocyanate) (pHDI) or poly(methylenediphenyldiisocyanate); ratio AE adduct dry weight/isocyanate dry weight constitutes from 10:1 to 1:1 and ratio soya/total content of AE adduct and isocyanate component in composition constitutes from 1:2 to 10:1. Isocyanate includes water-dispersible isocyanate. Invention also relates to method for obtaining composite, which includes the following stages: a) obtaining lignocelluloses substrate, b) application of said glue composition on substrate and c) exposure of substrate/glue combination at heating and under pressure, and method for obtaining composite, which includes the following stages: a) obtaining lignocelluloses substrate, b) application of isocyanate on substrate, c) application of AE adduct and soya mixture on substrate, where ratio AE adduct dry weight/isocyanate dry weight constitutes from 10:1 to 1:1 and ratio soya/total content of AE adduct component and isocyanate component in composition constitutes from 1:2 to 10:1, and d) exposure of substrate/glue combination at heating and under pressure. Preliminary dispersion of isocyanate on substrate before processing with said glue results in increased strength. Invention also describes lignocelluloses composite, including lignocelluloses substrate and glue composition in accordance with claimed invention.

EFFECT: composition improvement.

10 cl, 13 tbl, 38 ex

Description

FIELD OF THE INVENTION

The present invention provides adhesive compositions that include a combination of a protein source, an amine-epichlorohydrin adduct (AE), and isocyanate-functional material.

BACKGROUND OF THE INVENTION

Adhesives obtained from protein-containing soybean flour were first widely used in the 1920s (U.S. Patent Nos. 1813387, 1724695 and 1994050). Soy flour suitable for use in adhesives was obtained and is still being obtained by removing some or most of the oil from soybeans, and residual soybean meal is obtained, which is then ground, and extremely fine soybean flour is obtained. Hexane is typically used to extract most non-polar oils from crushed soybeans, although extrusion / extraction methods are also suitable for removing oils. The resulting soy flour is then denatured (i.e., the secondary, tertiary, and / or quaternary structure of the proteins is modified to expose additional polar functional groups capable of forming bonds) to the surface in the presence of an alkaline agent, and partially hydrolyze (i.e., break covalent bonds ), in this case adhesives are obtained for joining wooden parts in dry conditions. However, these past-developed soybean-based adhesives are characterized by low water resistance, and their use is strictly limited to interior decoration work, so they were mainly replaced with hydrocarbon-based adhesives, which are mainly based on formaldehyde. Recently, in industries where wood adhesives are used, there is a need for environmentally friendly products, such as products that are characterized by reduced levels of formaldehyde emissions. Attention was again focused on protein-based adhesives, provided that their water resistance was increased. Adhesives based on the amine-epichlorohydrin / soya adduct (“AE / soya”) satisfy the market demand for formaldehyde-free adhesives that comply with legislation governing formaldehyde emissions from wood products (California Air Resource Board), “AIRBORNE TOXIC CONTROL MEASURE TO REDUCE FORMALDEHYDE EMISSIONS FROM COMPOSITE WOOD PRODUCTS)), April 26, 2007, and the Formaldehyde Standards for Composite Wood Products Act, July 7, 2010), and meet the recommended standards for ec Responsible construction, such as the United States Green Building Council (USGBC) rating system for energy and environmental design (LEED). AE / soy based adhesives are also characterized by significantly increased water resistance compared to traditional soy based adhesives.

Amine-epichlorohydrin polymers (AE polymers) are used in combination with proteins as adhesives for wood products (U.S. Patents Nos. 7060798 and 7252735, U.S. Patent Applications 2008/0021187, 2008/0050602 and 2008/0292886). It has been established that AE / soybean combinations are effective and durable adhesives for plywood in commercial systems, characterized in both dry and wet conditions by significantly improved characteristics compared to traditional soy based adhesives. It has also been found that AE / soy based adhesives are effective substitutes for formaldehyde-based adhesives such as urea-formaldehyde adhesives. However, there are still some applications where the characteristics of these materials can be improved. First of all, the problem of these adhesives is the adhesive strength when bonding various types of wood. Some varieties of wood that may be difficult to glue include maple, pecans, and stained yellow birch. Other areas where the characteristics of AE / soy based adhesives may be advantageous in connection with further improvement include areas of higher flexural strength and higher strength when using these adhesives as chipboard binder resin or chipboard - medium density fiberboard (MDF), as well as to increase the overall adhesive strength in wet conditions. It is also desirable to reduce the content of AE additive in the adhesive based on AE / soy, as AE supplement is a more expensive ingredient compared to soy flour.

Wood adhesives based on a combination of soy and AE resins are widely known (U.S. Patent Nos. 3494750, 7252735, 7060798). A number of patent applications have been published that describe improvements to this technology, such as the use of low-viscosity polyamidoamine-epichlorohydrin (PAE) resins (patent application US No. 2008/0050602), the preparation and use of spray adhesives for particleboard and MDF (application for issuance US patent No. 2007/073771, 2009/0098387 and 2010/046898), as well as the use of additives against staining (application for the grant of US patent No. 2008/0292886). Although it has been found that AE / soy combinations are effective and durable adhesives for plywood, particleboard and MDF in commercial systems, there are still some applications where it is possible to improve the performance of these materials.

SUMMARY OF THE INVENTION

The present invention relates to an adhesive composition comprising a protein component, an AE adduct component and an isocyanate component. The present invention also relates to a composite and a method for producing a composite comprising a substrate and an adhesive composition of the present invention.

Adduct AE is the reaction product of epichlorohydrin with a material containing a functional amino group.

Surprisingly, it has been found that the adduct AE / protein / isocyanate combinations provide an improved bonding of hard-glued veneers, such as stained yellow birch, as well as an extremely high bonded, more easily bonded veneer with a lower total additive content in the adhesive compared to using the AE adduct in separately as an additive. According to the present invention, the AE adduct component and the isocyanate component are additives. An example of an adduct AE includes polyamidoamine-epichlorohydrin (PAE). In addition, it was found that when using the adduct AE / soy protein / isocyanate combinations as a binder for a particleboard or medium density fiberboard (MDF), an increased bending strength and increased strength are provided. The preferred protein source is soy.

It was also found that the use of isocyanate in an adhesive based on PAE / soy can provide a significant improvement in the adhesive properties of the adhesive. Water-dispersible aliphatic isocyanates are preferred over the use of aromatic isocyanates due to the fact that the compositions obtained using aliphatic isocyanates have a significantly lower viscosity compared to the compositions of aromatic isocyanates, but only one type of isocyanates has a beneficial effect.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides an adhesive composition comprising (a) a protein component, (b) an AE adduct component, and (c) an isocyanate component. The present invention also relates to a composite and a method for producing a composite comprising a substrate and an adhesive composition of the present invention.

The problem of using these adhesives is primarily in the adhesive strength of some hard-to-fasten wood grades. Some varieties of wood that may be difficult to glue include maple, pecans, and stained yellow birch. Other areas where the characteristics of AE / soy based adhesives may be advantageous in connection with further improvement include areas of higher flexural strength and higher strength when using these adhesives as chipboard binder resin or chipboard - medium density fiberboard (MDF), as well as to increase the overall adhesive strength in wet conditions. It is also desirable to reduce the content of AE additive in the adhesive based on AE / soy, as AE supplement is a more expensive ingredient compared to soy flour.

Suitable proteins for use in the present invention include casein, blood meal, feather meal, keratin, gelatin, collagen, gluten, wheat gluten (wheat protein), whey protein, Zein (corn protein), rape seed meal, sunflower meal and soy protein . A preferred protein is a plant-based protein.

The preferred protein source of the present invention is soy. Soy can be used in the form of isolates of soy protein, soy concentrates, soy flour, soybean meal or fried soy. Soybean flour suitable for use in adhesives can be obtained by removing some or most of the oil from the soybeans, and residual soybean meal is obtained, which is then ground, and extremely fine soybean flour is obtained. In accordance with the present invention, the term "soy protein" includes soy flour, unless otherwise specified.

Typically, hexane is used to extract most of the non-polar oils from the crushed soybeans, although extrusion / extraction methods are also suitable for removing the oils. Residual hexane in extracted soya flakes is usually removed by one of two processes: in a solvent removal unit (DT) or using a solvent stripping system in a gas pipe (flash distillation system (FDS)). In the DT process, soybeans are subjected to more significant heat treatment (maximum temperature is approximately 120 ° C, processing time is 45-70 min) compared to the FDS process (maximum temperature is approximately 70 ° C, processing time is 1-60 s). The DT process produces a darker product, commonly called soybean meal or fried soybean. These terms are used interchangeably, and they refer to soy products that have been processed in the DT process.

The ability to dissolve or disperse the protein fraction of the soy product in water is evaluated by the protein dispersibility index (PDI). This test can be described as follows: "to carry out the specified test, the sample of soybeans is ground, mixed at the specified ratio with water and ground at the specified speed (7500 rpm) for the specified time (10 min)." The nitrogen content in the crushed soybeans and in the extract is determined using a burning analysis method. The PDI value is the quotient of dividing the nitrogen content of the extract by the nitrogen content of the starting beans (Illinois Crop Improvement Association Inc., website: http://www.ilcrop.com/ipglab/soybtest/soybdesc.htm, available from 27 July 2008).

The protein fraction in soy products after DT treatment is characterized by lower solubility / dispersibility in water compared to soy products after FDS treatment, as follows from lower PDI values. The PDI values of soybean meal (fried soybean) are typically 20 or less, while the PDI values of soybean products after FDS processing range from 20 to 90.

Soy protein is usually obtained in the form of soy flour after grinding soy flakes and sifting through a sieve with a mesh size of 100-200 mesh. Soy flour can then be refined (usually by extraction of soluble hydrocarbons with a solvent), and a soy protein concentrate is obtained. Fat-free soybeans can then be peeled to produce soy protein isolate (SPI).

To increase the solubility, dispersibility and / or reactivity of the protein, it can be pre-processed or modified. Soy protein can be used immediately after preparation, or it can be further modified to improve its characteristics. In U.S. Patent No. 7060798, the contents of which are fully incorporated into the present description by reference, methods for modifying the protein and its inclusion in the adhesive are described. It is contemplated that a modified protein or modified soy flour can be used in the present invention. Another method for processing protein is to use effective modifiers, such as sodium metabisulfite, to formulate low viscosity formulations as described in U.S. Patent Application. No. 2010/0093896, the contents of which are fully incorporated into this description by reference.

Protein can also be solvated, denatured or dispersed with the addition of urea or non-urea diluents (patent applications U.S. No. 2007/073771, 2009/0098387 and 2010/046898). Basically, this treatment is used to obtain binders for particleboard or MDF.

A preferred type of soybean for use in the present invention is soybean flour with a PDI of 20 or more.

The AE adduct component of the present invention is typically a water-soluble material that contains a primary amine, a secondary amine that interacts with epichlorohydrin. Examples of certain polymers whose functionality can be enhanced by reaction with epichlorohydrin and which can be used according to the present invention include polyamidoamines, polydiallylamine, polyethyleneimine, polyvinylamine and chitosan.

A preferred class of AE adducts of the present invention are polyamidoamine-epichlorohydrin (PAE) resins. These polymers are characterized by the presence of a reactive azetidine group and a reactive amide group in the main chain. Functional azetidine group, which is a reactive fragment of these materials, provides their thermoset. Some particularly useful amine epichlorohydrin polymers include products under the trade names Hercules® CA1400, Hercules® CA1920A, Hercules® CA1000, and Hercules® CA1100 from Hercules Incorporated, Wilmington, Delaware, USA. PAE resins are widely known in the art, mainly for use as agents for imparting moisture resistance to paper products. Another type of PAE resins, which are primarily suitable for use in the present invention, is described in U.S. Patent Application. No. 2008/0050602.

AE adducts are available in the form of aqueous solutions, the solids content of which varies in the range from about 10% to about 60%.

Isocyanate polymers are highly reactive compounds that are widely used in adhesive systems, and are also widely used as components of wood glue compositions. The most commonly used isocyanate compounds are based on aromatic isocyanates such as methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI). Aliphatic isocyanates are also used, examples include, but are not limited to, hexamethylene diisocyanate (HDI) and isophorondiisocyanate (IPDI).

Isocyanate additives are generally known in the art and are widely used in adhesive formulations in monomeric, oligomeric and / or polymeric form. Most often, these isocyanates are used in polymer form. This provides faster curing, higher viscosity and increased safety during use (lower free monomer content). To ensure the function of an effective crosslinking agent, the isocyanate must contain at least two reactive isocyanate groups.

Suitable isocyanate additives that can be used in the present invention include any liquid or solid organic isocyanate containing at least two reactive isocyanate groups. Suitable isocyanate additives may contain aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanate groups. Mixtures of polyisocyanates are also suitable. The following are specific examples of suitable isocyanates: hexamethylene diisocyanate (GDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate (IPDI), bis (4-isocyanatocyclohexyl) methane (various hydrogenated diurethanes) including, for example, hexamethylene diisocyanate (a commercial product sold under the trade name Desmodur® by Bayer MaterialScience, Pittsburgh, PA, USA), urethdione derivatives of various diisocyanates, including, for example, hexamethi endisiocyanate and IPDI, isocyanurate derivatives of various diisocyanates, including, for example, hexamethylene diisocyanate (a commercial product sold under the trade name Desmodur® N 3390 by Bayer MaterialScience, Pittsburgh, PA, USA) and IPDI (a product sold under the trade name 18 polyisocyanate IPDI Huls America, Inc., Piscataway, New Jersey, USA) urethane adducts of diisocyanates with polyols such as, for example, ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol and the like, as well as oligomeric and poly measured polyols.

Isocyanates are also obtained in the form of water-dispersible formulations. A preferred type of isocyanate for use in the present invention is water dispersible isocyanate formulations. The basis of water-dispersible isocyanates is usually hexamethylenediisocyanate (GDI). Some examples of these materials include Bayhydur® 302, Bayhydur® 303 and Bayhydur® XP 2547 from Bayer MaterialScience, Pittsburgh, PA, USA, Easaqua® XM 501 and Easaqua® 502 from Perstorp, Cranbury, NY Jersey, USA, Dorus® R-400, available from Henkel Corporation, Elgin, Illinois, USA, and Basonat® F 200 WD, from BASF SE, Ludwigshafen, Germany.

The combination of AE resins and isocyanates in soy based adhesives provides a set of functional groups that lead to a synergistic improvement in adhesive properties.

The ratio of the protein component / total content of the AE adduct component and the isocyanate component in the composition can range from 1: 2 to about 1000: 1, preferably from about 1: 2 to about 100: 1, and most preferably from 1: 2 to 10: 1 based on dry weight. In some embodiments, the ratio is from about 1: 1 to about 100: 1, preferably from 1.5: 1 to about 15: 1.

The ratio of the adduct AE / isocyanate component in the composition can range from about 100: 1 to 1:10, more preferably from about 20: 1 to 1: 5, and even more preferably from 20: 1 to 1: 1, more preferably from 15 : 1 to 1: 1, most preferably from about 10: 1 to 1: 1. The preferred AE adduct is PAE.

The total solids content in the composition may vary from 5% to 75%, more preferably from 25% to 65%, and most preferably from 30% to 60%. In one preferred embodiment, the solids content of the composition is more than 25%, in another preferred embodiment, the solids content is more than 30%.

The compositions of the present invention are prepared by combining components (protein, AE adduct and isocyanate) in an aqueous medium. Material containing functional isocyanate groups can be added at any time during the process. In one embodiment of the present invention, the components are added simultaneously and then mixed. Adding isocyanate at the end of the mixing process allows you to get a product with a lower viscosity compared to the product obtained by adding isocyanate at the beginning of the process. Another way to use the isocyanate in the adhesive composition is to add the isocyanate to the soybean / adduct AE mixture immediately before use through the integrated mixer. After adding all the components, they are thoroughly mixed, and a homogeneous material is obtained. Additional materials, such as non-aqueous diluents or solvents, anti-foaming agents, viscosity modifiers, surfactants, as well as acids or bases used to adjust the pH, can be added to the composition. In yet another embodiment of the present invention, the soybean / adduct AE mixture and the isocyanate component are combined when applied to a substrate.

The pH of the composition of the present invention can range from about 4.5 to about 9, more preferably from about 5 to less than 8, and most preferably from about 5.5 to about 7.5. Lower pH values provide higher viscosity stability, however, it should be borne in mind that at too low pH values, the adhesive strength decreases and the curing rate is reduced to a greater extent.

The viscosity of the composition depends on the ratio of ingredients, total solids and final pH. Ultimately, viscosity limitation is equipment dependent. High viscosity materials require more powerful and more expensive mixers, pumps and processing equipment. Preferably, the viscosity is less than 200,000 cP (centipoise, as measured by a Brookfield viscometer at 10 rpm), more preferably less than 100,000 cP, even more preferably less than 50,000 cP. The viscosity can range from 100 cP to 200,000 cP, more preferably from 200 cP to 100,000 cP, and most preferably from 200 cP to 50,000 cP.

In another embodiment, the present invention provides the application of adhesive compositions for the production of composite wood materials and other composite materials. Compositions can be applied in a variety of ways, such as rotary coating, knife coating, extrusion, coating in bulk, foam coating, paddle mixers and spray coating machines, an example of which is a centrifugal resin coating machine. Despite the difference in requirements for different categories and types of applications, lower viscosity is an advantage when using these application technologies, especially for spraying adhesive compositions upon receipt of particleboard or MDF. Compositions with low viscosity, as a rule, are used to obtain particleboard and MDF, while compositions with a higher viscosity can be used to obtain plywood.

The adhesive composition of the present invention can be used in many industries. For example, the adhesive composition can be applied to a suitable substrate in an amount in the range from 1 wt.% To 25 wt.%, Preferably in the range from 1 wt.% To 10 wt.% And most preferably in the range from 2 wt.% To 8 wt. .% calculated on the dry weight of the substrate.

After applying the adhesive composition to the substrate, the adhesive / substrate combination is heated and pressed to form a composite.

Using the glue of the present invention, a number of materials can be produced, including particle board, oriented particle board (OSB), wafer board, fiber board (including medium density and high density fiber board), parallel strip wood (PSL ), oriented wood chips (LSL), structurally oriented lumber (OSL) and other similar products. In preparing the thermoset products of the present invention, lignocellulosic materials such as wood, wood pulp, straw (including rice, wheat or barley), flax, hemp, and sugarcane squeezes can be used.

Lignocellulosic product is usually obtained by mixing glue with a substrate, presented in the form of powders, particles, fibers, wood chips, flake fibers, coarse chips, scraps, shavings, sawdust, straw, stalks or bundles of fibers, followed by pressing and heating the resulting combination, whereby cured material. The moisture content of the lignocellulosic material before mixing with the adhesive of the present invention should be in the range of 2% to 20%.

The glue of the present invention can also be used to produce plywood or laminated plywood wood (LVL). For example, in one embodiment, the adhesive can be applied to veneer surfaces by rotational coating, knife coating, coating in bulk or by spraying. Then, a plurality of veneer sheets are stacked, and sheets of the required thickness are obtained. The mats or sheets are then placed in a press (for example, a flat press), usually heated and pressed to provide hardening and curing of the materials, and a plate is obtained. A fiberboard may be produced by a wet felt / wet pressing method, a dry felt / dry pressing method, or a wet felt / dry pressing method.

In addition to lignocellulosic substrates, adhesive compositions can be used with substrates such as glass wool, glass fiber and other inorganic materials. Adhesive compositions can also be used with combinations of lignocellulosic and inorganic substrates.

Examples

In examples 1-15, the viscosity and adhesion properties of adhesive compositions based on PAE / soy and compositions based on isocyanate / soy, and also compositions based on isocyanate / PAE / soy are compared and compared.

Comparison Example 1

In this comparison example, a dispersion of soy flour is described which is mixed in water with minor amounts of an antifoaming agent and sodium metabisulfite (MBSN) as a viscosity modifying agent. 140.00 g of deionized (DI) water, 0.80 g of MBSN (> 99%, Aldrich Chemical Company, Milwaukee, Wisconsin, USA) and 0.32 g of antifoam agent were added to a stainless steel beaker (600 ml volume) , Advantage 357 (manufactured by Hercules Incorporated, Wilmington, Delaware, USA). The mixture was stirred for 2 minutes with a paddle mixer attached to a mechanical mixer. While stirring in the mixer, 84.21 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. At this stage, the pH and viscosity of the preparations were measured. The sample was vigorously stirred for 30 s, then the viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm. The properties of this composition are given in table 1.

Comparison Example 2

In this comparison example, a dispersion of soybean flour mixed with PAE resin is described. 91.39 g of DI water, 70.00 g of Hercules® CA1920A product (20% aqueous solution of PAE solid resin manufactured by Hercules Incorporated, Wilmington, Delaware, USA) were added to a stainless steel laboratory glass (600 ml), 0 70 g of MBSN (> 99%, Aldrich Chemical Company, Milwaukee, Wisconsin, USA) and 0.32 g of antifoam agent, Advantage 357 (Hercules Incorporated, Wilmington, Delaware, USA), and the mixture was stirred for 2 minutes with paddle a mixer connected to a mechanical mixer. While stirring in the mixer, 73.68 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. At this stage, the pH and viscosity of the preparations were measured. The sample was vigorously stirred for 30 s, then the viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm. The properties of this composition are given in table 1.

Example 3

A dispersion of soy flour was obtained by adding polymethylene diphenyl diisocyanate (pMDI) in the same way as described in the comparison example. 134.95 g of DI water, 0.70 g of MBSN (> 99%, Aldrich Chemical Company, Milwaukee, Wisconsin, USA) and 0.28 g of anti-foaming agent, Advantage 357 were added to a stainless steel beaker (600 ml volume) (Hercules Incorporated, Wilmington, Delaware, USA), and the mixture was stirred for 2 minutes with a paddle mixer attached to a mechanical mixer. To the stirred mixture was added 7.00 g of Rubinate® 1840 PMDI (Huntsman Polyurethanes, Woodlands, Texas, USA) and stirred vigorously for 2 minutes. Stirring of the mixture was continued and 73.68 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. The properties of this composition are given in table 1.

Example 4

In this example, a formulation was prepared in the same manner as described in Example 3, except that instead of using the Rubinate® 1840 PMDI, Dorus® R-400 polyhexamethylene diisocyanate (PGDI) (Henkel Inc., Elgin, Illinois, USA) was used. The properties of this composition are given in table 1.

Example 5

In this example, the composition was obtained in the same manner as described in Example 3, except that instead of 7.00 g, 14.00 g of Rubinate® 1840 PMDI was used, and instead of 134.95 g, 147.39 g of DI water was used. The properties of this composition are given in table 1.

Example 6

In this example, the composition was obtained in the same manner as described in example 4, except that instead of 7.00 g, 14.00 g of Dorus® R-400 pGDI was used, and instead of 134.95 g, 147.39 g of DI water was used. The properties of this composition are given in table 1.

Example 7

120.95 g of DI water, 17.50 g of Hercules® CA1920A product (Hercules Incorporated, Wilmington, Delaware, USA), 0.70 g MBSN (> 99%, Aldrich) were added to a stainless steel laboratory glass (600 ml volume) Chemical Company, Milwaukee, Wisconsin, USA) and 0.28 g of antifoam agent, Advantage 357 (Hercules Incorporated, Wilmington, Delaware, USA), and the mixture was vigorously stirred for 2 minutes with a paddle mixer attached to a mechanical mixer. 3.50 g of Rubinate® 1840 PMDI (Huntsman Polyurethanes, Woodlands, Texas, USA) was added to the stirred mixture and mixed vigorously for 2 minutes. Stirring of the mixture was continued and 73.68 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. The properties of this composition are given in table 1.

Example 8

In this example, a formulation was prepared in the same manner as described in Example 7, except that instead of using the Rubinate® 1840 PMDI, the Dorus® R-400 PGDI (Henkel Inc., Elgin, Illinois, USA) was used. The properties of this composition are given in table 1.

Example 9

In this example, the composition was obtained in the same manner as described in example 7, except that 35.00 g of Hercules® CA1920A and 113.17 g of DI water were used. The properties of this composition are given in table 1.

Example 10

In this example, a formulation was prepared in the same manner as described in Example 9, except that instead of using the Rubinate® 1840 PMDI, the Dorus® R-400 PGDI (Henkel Inc., Elgin, Illinois, USA) was used. The properties of this composition are given in table 1.

Example 11

In this example, the composition was obtained in the same manner as described in example 8, except that 7.00 g of Dorus® R-400 PGDI (Henkel Inc., Elgin, Illinois, USA) and 127.17 g of DI water were used. The properties of this composition are given in table 1.

Example 12

In this example, the composition was obtained in the same manner as described in example 11, except that 35.00 g of Hercules® CA1920A and 119.39 g of DI water were used. The properties of this composition are given in table 1.

Example 13

Adhesive based on PAE / soy was obtained in the same way as described in example 2, except that used 35.00 g of the product Hercules® CA1920A and 106.95 g of DI water.

Example 14

Adhesive based on PAE / soy was obtained in the same way as described in example 2, except that 52.50 g of Hercules® CA1920A and 99.17 g of DI water were used.

Table 1 shows the viscosity values for examples of comparison and a number of adhesive compositions based on PAE / soy obtained with the addition of isocyanates. This study evaluated the effects of aromatic isocyanate (Rubinate® 1840 PMDI, manufactured by Huntsman Polyurethanes, Woodlands, Texas, USA) and water-dispersible aliphatic isocyanate (Dorus® R-400 PGDI, manufactured by Henkel Corp., Elgin, Illinois, USA) on the viscosity properties of compositions based on PAE / soy.

For a dispersion of soy flour in water (Example 1), an extremely small change in viscosity was observed over time. Example 2 is another comparison example, where the composition includes 20 dry parts of Hercules® CA1920A PAE resin per 100 parts of soybean (“h / 100 h”). For this composition, a lower viscosity was observed compared to soy flour separately, however, over time, the viscosity constantly increased and after 19 hours exceeded the viscosity of the aqueous dispersion of soy flour (example 1). Examples 3 and 4 compared the effects of aromatic isocyanate (pMDI) and aliphatic isocyanate (pGDI) added to soy flour at a concentration of 10 hours / 100 hours. The viscosity of the composition comprising aromatic isocyanate was more than an order of magnitude higher than the viscosity of the composition comprising aliphatic isocyanate while in this composition, gelation was observed after 24 hours, while the composition of the aliphatic isocyanate after 24 hours was still a liquid with a viscosity of 40,900 cP. Another comparison of aromatic isocyanate and aliphatic isocyanate mixed with soy flour is described in examples 5 and 6, where isocyanates were added at a concentration of 20 hours / 100 hours. For a composition containing 20 hours / 100 parts of PMDI (example 5), was observed an even higher viscosity compared to a composition containing 10 parts / 100 parts of PMDI (Example 3). In a composition containing 20 hours / 100 parts of pMDI, gelation was observed after about 6 hours. For comparison, the viscosity of a composition containing 20 parts / 100 parts of pGDI (Example 6) was 32 times lower than the viscosity of a composition containing 20 hours ./100 parts of PMDI, as well as lower viscosity of a composition containing 10 parts / 100 parts of PGDI (Example 4).

Examples 7-10 show a comparison of two different isocyanates in glue formulations containing soy flour and PAE resin. In the examples with odd numbers, pMDI was used, and in the examples with even numbers, pGDI was used. For the PGDI formulations, lower viscosity values and a lower rate of increase in viscosity over time were observed. Examples 11 and 12 are further examples of PAE / soy / pGDI formulations for which low initial viscosity values were observed and which still remained in a liquid state for 18-20 hours after preparation.

Table 1 Viscosity properties of adhesive compositions based on PAE / soy containing isocyanate additives (1) Example Number The content of PAE (hours / 100 hours) Type of Isocyanate The content of isocyanate (hours / 100 hours) Time (h) pH RV Vision (cP) Spindle / (rpm) one 0 No No 0.00 6.01 28,200 6/10 2.07 6.00 32,000 6/10 25.38 5.93 34,700 6/10 49.33 5.92 32,000 6/10 2 twenty No No 0.00 5.36 14,100 6/10 2.75 5.28 21,300 6/10 19.75 5.55 39,000 6/10 3 0 PMDI 10 0.00 5.85 132,000 7/10 1.00 5.80 573,300 7/10 23.49 - Gel 6/10 four 0 PGDI 10 0.00 6.03 11,300 6/10 7.33 6.18 23,000 6/10 24.22 6.10 40,900 6/10 5 0 PMDI twenty 0.00 5.87 242,700 6/10 5.47 - Gel 6/10 6 0 PGDI twenty 0.00 6.08 7,600 6/10 3,50 6.08 12,500 6/10 20.50 6.07 132,400 6/10 7 5 PMDI 5 0.00 5.69 66,700 6/10 3.20 5.62 165,200 7/10 8 5 PGDI 5 0.00 5.82 12,200 6/10 1,67 5.72 20,500 6/10 18.67 5.74 70,600 6/10 9 10 PMDI 5 0.00 5.51 74,400 6/10 2,31 5.46 174,000 7/10 10 10 PGDI 5 0.00 5.65 10,300 6/10 1,07 5.58 13,700 6/10 18.08 5.63 71,200 6/10 eleven 5 PGDI 10 0.00 5.92 10,300 6/10 6.68 5.89 40,900 6/10 23.57 5.80 107,600 6/10 12 10 PGDI 10 0.00 5.63 8,400 6/10 4.00 5.59 16,900 6/10 20.90 5.69 144,400 6/10

(1) All formulations included 36% solids and 1.0 hours / 100 hours MBSN. "Hours / 100 hours" refers to parts per 100 parts of soy.

Example 15

Plywood panels were prepared using the adhesive compositions described in Examples 1-14. These 3-ply panels were prepared from 12 inch x 12 inch poplar veneer sheets with an average thickness of 3.6 mm (0.14 inch). The veneer sheets were stored in a conditioning chamber at 80 ° F / 30% relative humidity for several days or more, then panels were prepared. Glue was applied on both sides of the central veneer sheet in an amount of 20-22 g / sq. foot. The direction of the fibers of adjacent veneer sheets is mutually perpendicular (90 °) along the thickness of the panel (in a typical plywood construction, the direction of the fibers of the central veneer sheet is perpendicular to the direction of the fibers of the outer and rear veneer sheets). The time for applying glue to complete the complete assembly of the products was 2-4 minutes. Three-layer prefabricated products with wet glue were placed under a 14-inch x 14-inch plate, on top of which 1 gallon of water was placed for 15 minutes (to simulate processing time in an industrial environment), then hot pressed. After the treatment period, the panels were hot pressed at 250 ° F and 125 psi. inch for 3 min. In this example, cold pressing was not used before the hot pressing step. The hot-pressed panels were held at 70 ° F / 50% relative humidity for 48 hours, then cut. Cut test samples were kept in a chamber at 70 ° F / 50% relative humidity for at least 24 hours, then a test was performed.

Dry and wet shear strength tests were performed according to the methodology of ASTM D-906 and EN-314 European Standard. Samples intended for shear tests in the wet state were soaked before testing at ambient temperature for 24 hours. All samples for shear tests were tested by fixing them in the fixture lock. For each condition, a total of 4 samples were tested for shear in the dry state and 6 samples for shear in the wet state.

The test of plywood panels with three soaking cycles was carried out according to the method of the standard of the American Association of Plywood Manufacturers ANSI / HPVA HP-1-2009 using 4 samples in each test. Samples intended for testing with three soaking cycles were also evaluated on a scale from 0 to 10 points, where 0 points corresponds to the complete absence of delamination of the adhesive joint, and 10 points corresponds to the complete delamination of the adhesive joint. A score of 6 points or more qualifies as non-compliance with the standard. A complete set of evaluation criteria is presented in Table 2.

table 2 Criteria for the evaluation of samples according to the test results with 3 soaking cycles Rating Compliance / Non-Compliance Features of the glue line 0 Yes Complete absence of delamination of the glue line one Yes Minimum delamination, <0.1 inches 2 Yes Minimum delamination, <0.25 inches 3 Yes Moderate delamination, <0.5 inches four Yes Moderate delamination, <1 inch 5 Yes Significant stratification, <2 inches 6 No Significant stratification, 2-3 inches 7 No Strong delamination, 3-4 inches 8 No Extremely strong lamination, 4-5 inches 9 No Almost complete veneer stratification 10 No Complete veneer stratification

Table 3 Properties of 3-layer poplar panels obtained using test compounds Glue Compositions Panel test Test with 3 cycles soaking Shear test Soder- Shift in Shift in Glue, Soder- burning The corresponding dry wet room number burning (h / 100 h) and authority condition RD *, condition RD note note PAE type of Wednesday standard (lbs / sq. dry (lbs / sq. wet. ra ra (h / 100 h) isocyanate point that% inch) (%) inch) (%) 15-A one 0 0 10.00 0% 106 one 0 0 15-in 13 10 0 0.50 one hundred% 316 78 130 3 15-C fourteen fifteen 0 3,50 25% 285 63 139 2 15-D 2 twenty 0 0.38 one hundred% 389 90 217 8 15th 3 0 10 pMDI 10.00 0% 254 54 0 0 15-f four 0 10 pgdi 10.00 0% 182 0 0 0 15-g 5 0 20 pMDI 2.00 75% 267 41 124 one 15-N 6 0 20 pgdi 10.00 0% 271 3 0 0 15-I 7 5 5 pMDI 5.50 0% 243 83 64 0 15-j 8 5 5 pgdi 4.00 25% 471 one hundred 104 0 15-k 9 10 5 pMDI 0.00 one hundred% 277 86 194 9 15-L 10 10 5 pgdi 0.00 one hundred% 455 one hundred 211 3 15-M eleven 5 10 pgdi 4.38 fifty% 312 66 93 0 15-n 12 10 10 pgdi 0.00 one hundred% 357 78 195 0

Examples 15-A, 15-B, 15-C, 15-D, 15-E, 15-F 15-Gh 15-H are examples of comparison.

The panels obtained using the compositions based on PAE / soybeans described in the comparison examples (examples 15-B, 15-C and 15-D) had improved properties compared to the panel obtained using the composition described in the comparison example 15- A, which contained only soy flour. For samples based on PAE / soybeans, improved results were obtained when tested with 3 soaking cycles. Although for the sample described in example 15-C, compliance with the standard was only 25%, its average score of 3.5 points indicates an improved result compared with a score of 10 points for the sample described in example 15-A, because a score of 10 points corresponds to the complete stratification of the test samples during the test. The values of the shear strength in the dry and wet state of the compositions based on PAE / soy significantly exceeded the values obtained for the composition containing only soy.

Most formulations containing soy flour and isocyanate that do not contain any PAEs (examples 15-E, 15-F, 15-G and 15-H) did not meet the standard when tested with 3 soaking cycles. For the composition described in Example 15-G containing 20 hours / 100 parts of PMDI, the standard compliance with the test with 3 soaking cycles was 75%, while for this group high shear strength values were observed, but extremely a high viscosity value (242,000 cP) and a significantly lower value of the shear strength in the wet state compared with the composition containing PAE at the same concentration described in example 15-D (124 compared to 217).

For all adhesive formulations containing 10 hours / 100 parts of PAE and 5 or 10 hours / 100 parts of isocyanate (Examples 15-K, 15-L and 15-N), 100% compliance with the standard was observed during testing and evaluation 0 points (complete absence of delamination). Dry and wet shear strength values were extremely high. For a composition containing 10 hours / 100 parts of PAE and 5 parts / 100 parts of isocyanate (Examples 15-K and 15-L), significantly higher wet shear strengths were observed compared to the adhesive composition, containing 15 hours / 100 hours of PAE (Example 15-B). For compositions containing 5 hours / 100 parts of PGDI, 5 and 10 hours / 100 hours of PAE (Examples 15-J and 15-M, respectively), extremely high values of the dry shear strength at 100% were obtained. destruction of dry wood, significantly higher values of the shear strength in the dry state compared with the composition of the adhesive containing 20 hours / 100 hours of PAE (example 15-D).

In examples 16-20, a comparison was made between the adhesive properties of the adhesive compositions based on PAE / soy and the adhesive compositions based on isocyanate / PAE / soy when used for bonding stained yellow birch, which is a hard-to-stick wood grade.

Comparison Example 16

This example is a comparison example, which describes a typical composition of the adhesive based on PAE / soy. 38.40 g of DI water, 57.00 g of Hercules® CA1100 product (Hercules Incorporated, Wilmington, Delaware, USA) and 0.27 g of MBSN were added to a stainless steel laboratory glass (600 ml volume). The specified mixture was stirred for 2 min with a paddle mixer attached to a mechanical mixer. Stirring was continued, and 48.00 g Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. The properties of this composition are given in table.4.

Comparison Example 17

This example is a comparison example, which describes a typical composition of the adhesive based on PAE / soy. 38.40 g of DI water, 57.00 g of Hercules CA1100 product (Hercules Incorporated, Wilmington, Delaware, USA), 3.70 glycerol (purity> 99%, Aldrich Chemical) were added to a stainless steel laboratory glass (600 ml volume) Co., Milwaukee, Wisconsin, USA) and 0.27 g of MBSN. The specified mixture was stirred for 2 min with a paddle mixer attached to a mechanical mixer. The mixture was kept stirring and 48.00 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. The properties of this composition are given in table.4.

Example 18

38.40 g of DI water, 57.00 g of Hercules CA1100 product (Hercules Incorporated, Wilmington, Delaware, USA) and 0.27 g of MBSN were added to a stainless steel laboratory glass (600 ml volume). The specified mixture was stirred for 2 min with a paddle mixer attached to a mechanical mixer. The mixture was kept stirring and 48.00 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. Then, 4.00 g of Dorus® R-400 pGDI (Henkel Inc., Elgin, Illinois, USA) was added to the mixture, and stirring was continued for another 2 minutes. The properties of this composition are given in table.4.

Example 19

38.40 g of DI water, 57.00 g of Hercules CA1100 product (Hercules Incorporated, Wilmington, Delaware, USA), 3.70 glycerol (purity> 99%, Aldrich Chemical) were added to a stainless steel laboratory glass (600 ml volume) Co., Milwaukee, Wisconsin, USA) and 0.27 g of MBSN. The specified mixture was stirred for 2 min with a paddle mixer attached to a mechanical mixer. The mixture was kept stirring and 48.00 g of Soyad® TS9200 soy flour (Hercules Incorporated, Wilmington, Delaware, USA) was added to the mixture. After adding all the soy flour, vigorous stirring was continued for 8 minutes. Then, 8.25 g of Dorus® R-400 PGDI (Henkel Inc., Elgin, Illinois, USA) was added to the mixture, and stirring was continued for another 2 minutes. The properties of this composition are given in table.4.

Example 20

To obtain plywood panels intended for testing, received the adhesive compositions described in examples 16-19. Plywood panels were 3-layer panels, including the stained yellow birch (RUV) / eucalyptus / poplar design. Glue was applied on both sides of the central veneer sheet in an amount of 18 to 20 g / sq. foot. The direction of the fibers of adjacent veneer sheets is mutually perpendicular (90 °) along the thickness of the panel (the direction of the fibers of the central veneer sheet is perpendicular to the direction of the fibers of the outer and rear veneer sheets). Three-layer prefabricated products with wet glue were placed under a 14 inch x 14 inch plate on top of which 1 gallon of water was placed for 10 minutes (processing time), then cold pressed. The panels were cold pressed at a pressure of 83 psi. inch for 5 min. At the end of cold pressing, the stickiness of the panels was evaluated using a quality scale from 0 points (extremely weak stickiness and extremely weak bonding of the panel) to 5 points (high stickiness and high bonding of the panel). After cold pressing, the panels were hot pressed at 230 ° F and a pressure of 153 psi. inch for 4 min. The panels were held at 70 ° F / 50% relative humidity for 48 hours, then cut. After the test samples were cut, they were kept in a chamber at 70 ° F / 50% relative humidity for at least 24 hours, then a test was performed.

The test of these panels with 3 cycles of soaking was carried out as described above. The strength of the dry adhesive joint (DBE) was also evaluated by the FYB / poplar adhesive joint (joint 1). The test according to this method was carried out by separating the glued veneer sheets using a knife and qualitatively assessing the strength of the adhesive joint and the amount of delaminated wood using a DBE scale of 0 to 5 points. In the indicated DBE scale, 0 points corresponds to an extremely weak adhesive joint, which can be disconnected with minimal strength, while no destruction of wood is observed, while a score of 5 points corresponds to a high-strength adhesive joint, for the destruction of which considerable strength is required, and 100% wood destruction. The test results of the panels are given in table.4.

Table 4 Compositions based on PAE / soybeans / PGDI and properties of FYB / eucalyptus / poplar Glue Compositions Panel Properties General But- Add- contains 3 cycles measures Glue, flaxen burning Glue- DBE soaking pane number Glice PGDI solid Viscosity bone the seam conformity whether an example rin (h / 100 h) substances (1), cP pH (2) 13) standard,% Example 20A comparisons 16 No No 39.90% 56,400 5.54 four 1.75 0% Example 20V comparisons 17 2,50% No 41.40% 45,700 5.39 four 2.25 0% 20C eighteen No 8.8 41.50% 26,800 5.50 four 4.25 one hundred% 20D 19 2.40% 18.1 44.60% 22,450 5.47 5- 5.00 one hundred%

(1) The viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm.

(2) Tack was evaluated on a scale of 0 to 5 points, where 1 point indicates extremely low tack and 5 points indicates high tack.

(3) “DBE, joint 1” refers to the strength rating of a dry adhesive joint (adhesive joint 1 — FYB / eucalyptus). Dry adhesive bonding was characterized by qualitatively assessing the resistance of wood to delamination and destruction on a scale from 0 to 5 points, where 0 points denotes extremely low adhesiveness without delamination of wood, and 5 points denotes high adhesiveness and almost 100% delamination of wood.

As a result of tests in the field and laboratory conditions, it was found that adhesives based on PAE / soy and standard urea-formaldehyde resins do not provide a strong connection of veneered stained yellow birch.

Examples of panels 20-A and 20-B were obtained using typical PAE / soya adhesive formulations used for plywood or composite wood flooring described in the examples of comparison. Examples of panels 20-C and 20-D were obtained using adhesive compositions that contained 8.8 and 18.1 hours / 100 parts of PGDI, respectively, and they had lower viscosity values compared to the panels obtained as described in comparison examples. The tack was a sufficiently high or higher value compared to the compositions obtained in the comparison examples, and the results of the dry adhesive strength test (DBE) for the compositions containing isocyanates were significantly higher compared to the results obtained for the compositions obtained in the comparison examples , which testified to a significant improvement in the strength of the adhesive joint compared to the system based on PAE / soy. Testing the panels by ANSI / HPVA HP-1-2009 with 3 cycles of soaking showed a significant difference between the compositions of the comparison and experimental examples of panels made using pgdi in addition to PAE resin. For the panels described in the comparison examples, complete failure was observed during the test with 3 soaking cycles, while the panels obtained using formulations that contained pGDI met the 100% standard during testing, which once again testified to a significant improvement in adhesive strength compared to a PAE / soy based system.

Evaluation of the strength of the dry adhesive bonding (DBE) of these panels at the glue line 1 (bonding of stained yellow birch and eucalyptus) also indicated an unexpected difference between the comparison examples and the compositions of the present invention. DBE values for panels made using comparison formulations (Examples 20-A and 20-B) were 1.75 and 2.25, while DBE values for panels made using compositions made of the present invention (Examples 20- C and 20-D), amounted to 4.25 and 5.00, which indicated an unexpected difference in the quality of the adhesive joint and the destruction of wood. For comparative examples, an extremely slight destruction of wood was observed, while for the examples of the present invention, almost complete destruction of wood was observed for joining stained yellow birch and eucalyptus, which once again testified to a significant improvement in adhesive strength compared to the PAE / soy system .

In examples 21-27, the viscosity and characteristics of a number of adhesive compositions based on PAE / soy, isocyanate / soy and isocyanate / PAE / soy were compared and contrasted when used to produce 3-layer poplar panels without a cold pressing step.

Examples 21 to 26

In these examples, formulations were prepared by mixing various amounts of water, PAE resin, isocyanate, soy flour, sodium metabisulfite and an anti-foaming agent. The exact amounts of additives used in these examples are given in table 5. Examples 21 and 22 are examples of comparison. The compositions in these examples were prepared by adding DI water, optionally Hercules® CA1920A PAE (manufactured by Hercules Incorporated, Wilmington, Delaware, USA) and MBSN into a laboratory stainless steel beaker (600 ml) and stirring intensively for approximately 1 min Soyad® TS9200 soy flour (manufactured by Hercules Incorporated, Wilmington, Delaware, USA) was added to the stirred mixture, then the combination was vigorously mixed for 8 minutes. If necessary, the PGSI Dorus® R-400 isocyanate was then added to these formulations and the resulting mixture was stirred for another 2 minutes. At this point, the pH and viscosity of the preparations were determined. Viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm. The indicated values are given in table 5.

Table 5 Examples
21-26 Soy flour TS9200 (g) PAE CA1920A (g) Dorus R-400 (g) MBSN (g) Anti-foaming agent A-357 (g) CI water (g) pH Viscosity (cP) (1) Comparison Example 21 73.68 0.00 7.00 0.70 0.28 134.95 5.82 12,200 Comparison Example 22 73.68 0.00 14.00 0.70 0.28 147.39 5.65 10,300 23 73.68 17.50 3,50 0.70 0.28 120.95 6.03 11,300 24 73.68 35.00 3,50 0.70 0.28 113.17 5.92 10,300 25 73.68 17.50 7.00 0.70 0.28 127.17 5.63 8,400 26 73.68 35.00 7.00 0.70 0.28 119.39 6.08 7,600

1) The viscosity was determined using a Brookfield viscometer RV, spindle No. 6, at 10 rpm

For formulations containing combinations of PAE resin and isocyanate, lower viscosity was observed compared to the viscosity of formulations containing only PAE resin.

Example 27

Plywood panels were prepared using the adhesive compositions described in Examples 21-26. These 3-ply panels were prepared from 12 inch x 12 inch poplar veneer sheets with an average thickness of 3.6 mm (0.14 inch). Prior to the manufacture of the panels, the veneer sheets were stored in a conditioning chamber at 80 ° F / 30% relative humidity. Glue was applied on both sides of the central veneer sheet in an amount of 20-22 g / sq. ft., the direction of the fibers of adjacent veneer sheets is mutually perpendicular (90 °) along the thickness of the panel (the direction of the fibers of the central veneer sheet is perpendicular to the direction of the fibers of the outer and rear veneer sheets). Three-layer prefabricated products with wet glue were placed under a 14 inch x 14 inch plate on top of which 1 gallon of water was placed for 15 minutes (processing time), then hot pressed. The cold method of pressing said panels was not used prior to hot pressing. After a period of processing time, the panels were hot pressed at 250 ° F and 125 psi. inch for 3 min. The panels were held at 70 ° F / 50% relative humidity for 48 hours, then cut. Cut test samples were kept in a chamber at 70 ° F / 50% relative humidity for at least 24 hours, then a test was performed.

The test with three cycles of soaking, the assessment of the tensile strength of the shear in the dry and wet state was carried out as described above. The test results of these panels are presented in table.6.

Table 6 Properties of the panels obtained using the compositions described in examples 2, 13, 14 and 21-26 Getting panels Panel Testing 3-cycle soaking Shear Strength Test Glue, example number PAE (h / 100 h) PGDI (h / 100 h) Wednesday point Compliance with the standard (%) Dry Shift (psi) RD is dry. (%) Wet Shift (psi) RD wet. % 15-in Comparison Example 3 10 0 0.50 one hundred% 316 78 130 3 15-C Comparison Example 14 fifteen 0 3,50 25% 285 63 139 2 15-D Example
comparisons 2 twenty 0 0.38 one hundred% 389 90 217 8 27-a Comparison Example 21 0 10 10.00 0% 182 0 0 0 27-B Comparison Example 22 0 twenty 10.00 0% 271 3 0 0 27-C 23 5 5 4.00 25% 471 one hundred 104 0 27-D 24 10 5 0.00 one hundred% 455 one hundred 211 3 27th 25 5 10 4.38 fifty% 312 66 93 0 27-f 26 10 10 0.00 one hundred% 357 78 195 0

For the panels described in examples 27-A and 27-B (obtained using the adhesive compositions described in comparative examples 21 and 22), it was found that when using isocyanate as the only additive (in the absence of PAE), extremely low test results are observed with 3 soaking cycles and extremely low wet shear strength characteristics, while dry shear strength characteristics are lower than those obtained when using a separate PAE additive (examples of panels 1 5-B, 15-C and 15-D) and combinations of PAE and isocyanate (Examples 27-C - 27-F). In Examples 27-C-27-F, a number of combinations of PAE and isocyanate were tested. In Examples 27-C and 27-D, for the combination of PAE and isocyanate, extremely high dry shear strength and dry wood failure values were observed. For Example 27-D, extremely high test results with 3 soaking cycles and extremely high wet shear strength were also observed. These results indicate that the combination of PAE and isocyanate can provide improved properties compared to using an equivalent amount of PAE separately (comparison of examples 27-D and 15-C). However, to ensure high adhesive properties, the PAE / isocyanate ratio is also important, despite the fact that in Example 27-D extremely high adhesive properties were observed with a PAE / isocyanate ratio of 10: 5, with a PAE / isocyanate ratio of 5:10, the adhesive properties of the composition, described in example 27-E, significantly reduced.

Examples 28-32 compare the stickiness of adhesive compositions based on PAE / soy and adhesive compositions based on isocyanate / PAE / soy when used for bonding stained yellow birch, which is a hard-to-stick wood grade.

Examples 28-32

In these examples, the compositions were obtained by mixing various amounts of water, PAE, isocyanate, soy flour, sodium metabisulfite and anti-foaming agent. The exact amounts of additives used in these examples are given in table.7. Example 36 is a comparison example in which only a PAE additive was used. These formulations were prepared by adding DI water, Hercules® CA1920A PAE (manufactured by Hercules Incorporated, Wilmington, Delaware, USA) into a laboratory stainless steel beaker (600 ml volume), MBSN and stirring vigorously for approximately 1 min. Soyad® TS9200 soy flour (manufactured by Hercules Incorporated, Wilmington, Delaware, USA) was added to the stirred mixture, then the combination was vigorously mixed for 8 minutes. If necessary, the PGSI Dorus® R-400 isocyanate was then added to these formulations and the resulting mixture was stirred for another 2 minutes. At this point, the pH and viscosity of the preparations were determined. Viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm. The indicated values are given in table.7.

Table 7 Examples
28-32 Soy flour TS9200 (g) PAE
CA1920A (g) PGDI Dorus R-400 (g) MBSN (g) Anti-foaming agent A-357 (g) CI water (g) pH Viscosity (cP) (1) 28 73.68 87.50 0.00 0.70 0.28 83.61 5.13 20,100 29th 73.68 35.00 3,50 0.70 0.28 113.20 5.62 14,800 thirty 73.68 52.50 3,50 0.70 0.28 105.40 5.47 12,900 31 73.68 70.00 1.75 0.70 0.28 94.50 5.31 13,300 32 73.68 70.00 3,50 0.70 0.28 97.61 5.30 11,900

(1) The viscosity was determined using a Brookfield RV viscometer, spindle No. 6, at 10 rpm.

Example 33

Plywood panels were prepared using the adhesive compositions described in Examples 28-32. These 3-ply panels were prepared from 12 inch x 12 inch veneer sheets. The panel construction consisted of a front sheet of stained yellow birch veneer (FYB), a central sheet of eucalyptus veneer and a back sheet of poplar veneer. Prior to the manufacture of the panels, the veneer sheets were stored in a conditioning chamber at 80 ° F / 30% relative humidity. Glue was applied on both sides of the central veneer sheet in an amount of 20-22 g / sq. ft., the direction of the fibers of adjacent veneer sheets is mutually perpendicular (90 °) along the thickness of the panel (the direction of the fibers of the central veneer sheet is perpendicular to the direction of the fibers of the outer and rear veneer sheets). Three-layer prefabricated products with wet glue were placed under a 14 inch x 14 inch plate on top of which 1 gallon of water was placed for 15 minutes (processing time), then hot pressed. After a treatment period, the panels were cold pressed at a pressure of 100 psi. inch for 10 min. Tack was rated on a scale of 0 to 5 above, then the panels were hot pressed at 250 ° F and 125 psi. inch for 3 min. The panels were held at 70 ° F / 50% relative humidity for 48 hours, then cut. Cut test samples were kept in a chamber at 70 ° F / 50% relative humidity for at least 24 hours, then a test was performed.

A test with three soaking cycles and an assessment of the strength of the dry adhesive joint along the FYB-eucalyptus joint (joint 1) was carried out as described above. The test results of these panels are given in table.8.

Table 8 Properties of the panels obtained using the adhesive compositions described in examples 28-32 Getting panels Panel Testing Example Number Glue, example number PAE (h / 100 h) PGDI (h / 100 h) Tack seam 1 / seam 2 (1) 3 soaking cycles DBE Seam grade 1 Compliance with the standard (%) DBE, seam 1 33-a Comparison Example 28 25 0 3/5 9.50 0% 2.0 33-b 29th 5 5 4/5 2,33 one hundred% 2.5 33-c thirty 10 5 4/5 0.00 one hundred% 2.6 33-D 31 twenty 2.5 5/5 2.67 one hundred% 4.0 33-e 32 twenty 5 5/5 0.00 one hundred% 5,0

The presented results indicate a significant difference between the glue described in the 33-A comparison example containing only the PAE additive and the adhesive compositions described in the examples, which contained both PAE and isocyanate additives. The adhesiveness of the adhesive described in Example 33-A at seam 1 (FYB-eucalyptus) was only 3 points, while the adhesiveness of all the adhesive compositions of the present invention for this seam was 4 and 5 points. While the percentage of compliance with the standard when tested with 3 soaking cycles for the composition described in example 33-A was 0%, the standard compliance of all panels obtained using the adhesive compositions of the present invention was 100%. The evaluation of the composition obtained in comparison example 36, when tested with 3 soaking cycles for seam 1, was 9.5 points (the lowest rating on this scale corresponds to 10 points, i.e., complete separation and separation of veneer sheets), while while for all the adhesive compositions described in the examples of the glue of the present invention, the score was less than 3 points, and the score for two of these compositions is 0 points (complete absence of delamination). Evaluation of the strength of the dry adhesive bonding (DBE) along the seam 1 also testified to a significant difference in the comparison example from the examples of the present invention. In the comparison example, the DBE score at seam 1 was 2.0 points. For all the adhesive compositions of the present invention with various combinations of PAE and isocyanates, higher DBE values are obtained. This is primarily unexpected due to the fact that in most of the compositions of the present invention used a lower total amount of additives. During the DBE test in Examples 33-D and 33-E, the values were 4.0 and 5.0 points, respectively, and extremely high levels of wood breakdown were observed. High DBE values are critical for commercial flooring or decorative plywood.

Example 34

Add GDI and MDI and processing time

In these examples, the advantage of adding two different isocyanates, hexamethylenediisocyanate (GDI) and methylene diphenyl diisocyanate (MDI), to the composition of soy based glue to produce a particle board is demonstrated. Polymeric MDI (pGDI), a commercial product sold under the trade name Dorus R-400 by Henkel, was used as a GDI, and polymeric MDI (PMDI), a commercial product sold under the trade name Runbinate 1840 by Huntsman, was used as a MDI.

As the particleboard mass used the mass for the "core" of particleboard obtained from the mill. The mass for the core is more coarse than the mass for the "front layer", which is known to specialists in this field of technology.

Used soya mixture was obtained at a ratio of 1 part soy flour Prolia 200/90 company Cargill / 1.33 parts of glycerol. Soy was mixed with water (sufficient to produce a final product containing 61% solids), an anti-foaming agent, Advantage 357, Ashland (0.004 parts), biocide (methylene bistiocyanate, 0.0003 parts) and sodium metabisulfite (0.013 parts).

As the PAE resin, a low molecular weight resin containing 55% solids was used. This type of resin is described in U.S. Patent Application. No. 13/020069, filed February 3, 2011

The soybean mixture (100 parts dry basis) was thoroughly mixed with PAE (30 parts dry basis). GDI (5 parts) was added to the MDI sample and mixed thoroughly, and MDI (10 parts) was added to the MDI samples and mixed thoroughly. Various wood processing compositions were prepared and used for 10 minutes. Intensive mixing was used.

The wood pulp was placed in a Bosch Univeral mixer, 800 W, which provided mixing in the mixing bowl, as well as continuous "turning" of the wood. Used a mixer with blades of the type of blades for shortcrust pastry ("cookie dough") with a minimum speed of mixing. While stirring the pulp, a stream of each glue composition was sprayed onto it. The spraying time was approximately 1 minute. For 100 parts of wood (dry base), 8 parts of glue (dry base) were added. The moisture content of the wood was approximately 3.7%, which is typical of the wood used in chipboard mills. Water was added to the adhesive compositions, while providing the same final moisture content in all boards equal to 10.5 parts of moisture / 100 parts of dry wood. After spraying, the wood was alter for another 30 s.

The treated wood was immediately placed in a rectangular forming machine with an internal size of 10 inches x 10 inches. Wood (525 g dry raw base) was added, which was sufficient to produce a slab with a final thickness of ½ inch with a density of approximately 55 pounds / cubic meter. foot. The wood in the forming machine was leveled and cold pressed at a pressure of 100 psi. inch, while receiving a molded mat, characterized by a certain degree of solidity. The form was removed. The mat obtained on the press plate was then transferred to a hot press. The upper press plate was placed on it and the structure was pressed at a pressing temperature of 160 ° C for 4 minutes starting from the time when the press reached the press shims (½ inch) near the molded structure. If possible, the press was quickly closed, sequentially for each sample. After pressing, the composites were removed from the press, the press plates were removed, and each obtained plate was cooled for 15 minutes under the same conditions, then folded.

The next day, the plates were cut into pieces measuring 8 inches x 1 inch, each piece was treated in the same way. Eight test pieces were cut from each sample. The dimensions of the slab were determined and, for each sample, the flexural strength (MOR) was determined in a 3-point bending test. For each sample, the strength values obtained for 8 pieces were averaged, and a 90% statistical confidence interval was determined. The results of determining the strength are shown in the upper part of table.9. The viscosity and pH values for the final adhesive compositions are also listed. The differences are minor.

The addition of MDI and MDI significantly increases the strength of the plates compared to control samples that do not contain MDI or MDI.

Table 9 Example 34 Description Mor glue pH Adhesive viscosity 34A Control, without DRO or MDI 2118 5.47 210 34B +5 GDI, no aging 2323 5.49 300 34C +10 MDI, no aging 2602 5.44 250 34D +5 GDI, holding for 60 minutes 2368 5.42 220 34E +5 GDI, holding 120 min 2343 5.39 200 34F +10 MDI, holding for 60 minutes 2511 5.39 230

In the same series of experiments, the adhesive compositions were kept after mixing and before spraying to reveal any negative effect of HDI or MDI on the shelf life of the adhesive in the container. Before use, the composition of the GDI was kept for 60 minutes and 120 minutes. The MDI composition was kept for 60 min. Within the range of experimental data, maintaining the composition of the GDI did not affect its characteristics. Maintaining the composition of MDI led to a slight decrease in performance, but the composition was still characterized by a significant advantage compared with the control image.

Example 35

Change in the content of DRO

In this example, the advantage of adding four different types of polyhexamethylene diisocyanate (pGDI) to the composition of soy based glue to produce a particle board is shown. Bayhydur 302, Bayhydur 303 and Bayhydur 2547 from Bayer and Easaqua MX 501 from Perstorp were used as GDI.

As the particleboard mass used the mass for the "core" of particleboard obtained from the mill. The mass for the core is more coarse than the mass for the "front layer", which is known to specialists in this field of technology.

Used soy mixture was obtained at a ratio of 1 part soy flour Prolia 200/90 company Cargill / 0.5 parts glycerol / 0.5 parts urea. Soy was mixed with water (sufficient to produce a final product containing 50% solids), an anti-foaming agent, Advantage 357, Ashland (0.004 parts) and sodium metabisulfite (0.013 parts) and acidified to pH 4.0 using sulfuric acid acids.

As the PAE resin, a low molecular weight resin containing 55% solids was used. This type of resin is described in U.S. Patent Application. No. 13/020069, filed February 3, 2011

The soybean mixture (100 parts dry basis) was thoroughly mixed with PAE (30 parts dry basis). At this point, GDI (5 parts) was added and thoroughly mixed. Various wood processing compositions were prepared and used for 10 minutes. Then the wood pulp was processed and received the slab, as described in example 1.

The next day, the plates were cut into pieces of size 8 inches × 1 inch, each piece was processed in the same way. Eight test pieces were cut from each sample. The dimensions of the slab were determined and, for each sample, the flexural strength (MOR) was determined in a 3-point bending test. For each sample, the strength values obtained for 8 pieces were averaged, and a 95% statistical confidence interval was determined. The strength results are shown in the upper part of Table 10.

Adding HDI significantly increases the strength of the plates compared to control samples that do not contain HDI. This is primarily true for the products Bayhydur 302, Bayhydur 2547 and Easaqua XM 501.

Table 10      Example 35 Interpolated MOR value (psi) NCO wt.% Viscosity NCO (cP) Control (without DRO) 1541 - - Bayhydur 303 1660 19.3 2400 Bayhydur 302 1727 17.3 2300 Bayhydur XP 2547 1782 23 600 EASAQUAXM 501 1781 21 1100

Example 36

Dependence of MOR on the addition of GDI

In the indicated example, the performance improvement observed when adding hexamethylenediisocyanate (GDI) to the composition of soya based adhesive at three different concentrations to produce a particle board was demonstrated. As GDI, pGDI, sold under the trade name Bayhydur 302 by Bayer, was used.

As the particleboard mass used the mass for the "core" of particleboard obtained from the mill. The largest pieces were removed using a sieve with a mesh size of 2 mm, and a homogeneous material was obtained. The mass for the core is more coarse than the mass for the "front layer", which is known to specialists in this field of technology.

Used the same content of soy and PAE in the glue, as described in example 44.

The soybean mixture (100 parts dry basis) was thoroughly mixed with PAE (20 parts dry basis). 2.5, 5.0, and 7.5 parts of GDI, respectively, were added to the GDI samples. The obtained adhesive samples were intensively mixed and various compositions were used for wood processing for 10 min. Intensive mixing was used.

The wood pulp was processed and the boards were obtained as described in Example 43. Adhesive (6.5 parts of a dry base) was added to the wood (100 parts of a dry base). The moisture content of the wood was approximately 2.0%, which is typical of wood used in chipboard mills. Water was added to the adhesive compositions, while ensuring the same final moisture content of all boards equal to 8.05 parts of moisture / 100 parts of dry wood. After hot pressing, the composites were removed from the press, the press plates were removed and each plate was cooled under the same conditions, then they were kept at equilibrium at a constant temperature of 21 ° C and 50% relative humidity for one week.

The plates were cut into pieces measuring 8 inches x 1 inch, each piece was treated in the same way. Eight test pieces were cut from each sample. The dimensions of the slab were determined and, for each sample, the flexural strength (MOR) was determined in a 3-point bending test. For each sample, the strength values obtained for 8 pieces were averaged, and a 90% statistical confidence interval was determined. The results of determining the strength are shown in the upper part of table.11.

Adding GDI significantly increases the strength of the plates compared to a control sample that does not contain GDI.

Table 11 Description (example 36) Mor Control, without DRO (glue 6.5 ppm) 1514 +2.5 GDI (glue 6.5 h / h) 1641 + 5.0 GDI (glue 6.5 h / h) 1722 +7.5 GDI (glue 6.5 h / h) 1799 Control, without DRO (glue 8.5 h / h) 1885 +2.5 GDI (glue 8.5 h / h) 2101 +7.5 GDI (glue 8.5 h / h) 2147

In this experiment, various glue compositions were also compared containing soy mixture (100 parts of a dry base), PAE (30 parts of a dry base), 0, 2.5 and 7.5 parts of HDI, respectively. In these samples, the treated mass contained 8.5 parts of glue / 100 parts of dry wood (glue 8.5 hours / 100 hours). 478 g of wood (dry untreated base) was added, which was sufficient to produce a slab with a final thickness of ½ inch with a density of approximately 45 pounds / cubic meter. foot.

All values given in Table 11 are the average values from the test results of two plates, with the exception of the example "+7.5 GDI (glue 6.5 hours / 100 hours)", in which one plate was tested.

Both at a higher adhesive content and at a lower adhesive content, an increase in MOR is observed as the content of HDI increases.

Example 37

Partial replacement of PAE with GDI

In the previous examples, the advantage of adding PGDI to the composition of soy based glue was shown. In this example, it was demonstrated that the PAE in the composition of soy-based glue can be replaced with HDI and still provide increased strength. The example describes the preparation of chipboard. The product Bayhydur 302 was used as GDI. Soy and PAE were used as described in Example 35.

The particleboard for the face layer was used and 10-inch particleboard samples were obtained as described in Example 34, with some differences. Glue (8.0 parts dry basis) was mixed with wood (100 parts dry basis). The solids content in the glue composition for each sample was adjusted by adding water to the final moisture content in the treated wood to 10.5 parts / 100 parts of dry wood. 461 g of wood (dry untreated base) was added, which was sufficient to produce a slab with a final thickness of ½ inch with a density of approximately 44.5 lbs / cubic meter. foot. The plate was hot pressed at 170 ° C for 3 minutes. Final plates were prepared and tested as described in Example 43.

In the control sample, the soybean mixture (100 parts of a dry base) was thoroughly mixed with PAE (20 parts of a dry base). In samples containing HDI, 2.5, 5.0, 7.5, or 10 parts of PAE were replaced with HDI. The obtained adhesive samples were intensively mixed and various compositions were used for wood processing for 10 min.

Table 12 Description (example 37) Mor Internal adhesive Control, without DRO 1770 101 2.5 parts of PAE were replaced by GDI 1841 118 5.0 parts of PAE were replaced by GDI 1872 129 7.5 parts of PAE were replaced by GDI 2052 129 10 parts of PAE were replaced by GDI 2106 142

When replacing PAE with GDI, the MOR values increase significantly. MOR values were obtained by averaging the test results of 16 pieces obtained from two plates for each sample. The same trend of MOR was observed regardless of the application of the uncorrected MOR value or the MOR value interpolated to the board density of 44.44 lbs / cc. foot.

The strength of the internal adhesive bond was also determined for these samples. For each sample, the average value was determined for 12 pieces obtained from two plates. The strength of the internal adhesive joint (IB) was determined for samples with a size of 1 inch × 1 inch, gluing samples with the front sides between two aluminum blocks. Then, the samples were disconnected, stretching along the z axis (with the front sides from each other), and the force at failure was recorded. Although there is a greater spread of data in determining IB than in determining MOR values, a similar trend is observed. The addition of HDI increases strength.

Example 38

GDI pre-spraying

In this example, it was demonstrated that preliminary spraying of isocyanate onto the wood before processing the wood with glue based on soybean still leads to an increase in strength. The example describes the preparation of chipboard. As GDI, the product Dorus R-400, as described above, was used.

A core particleboard was used and 10-inch particleboard samples were obtained as described in Example 34, with some differences. The final moisture content of the treated wood was 8.7 parts / 100 parts of dry wood. The plate was hot pressed at 170 ° C for 3 minutes. A portion of soybean in the composition of the adhesive was obtained in the following proportions: 2 parts of Cargill soy flour Prolia 200/90 / 1 part of glycerin / 1 part of urea. Soy was mixed with water (sufficient to produce a final product containing 55% solids), an anti-foaming agent, Advantage 357, Ashland (0.008 parts), biocide (methylene bistiocyanate, 0.0006 parts) and sodium metabisulfite (0 , 02 parts). The pH of the mixture was reduced to 3.8 with vigorous stirring using a concentrated solution of sulfuric acid. Then, urea was added with stirring.

The pulp was placed in a Bosch Univeral mixer, as described in Example 34. With the stirring of the pulp, a DRO stream was sprayed onto it. Then sprayed the rest of the glue. The specified sample was compared with a sample of glue that did not contain GDI, as well as with glue to which GDI was added before spraying, as described in Example 34. The MOR values are shown in Table 13. In addition to determining MOR, the MOR values were presented as a graph of the density of each sample (a correlation between density and strength is observed). The plot data were approximated in a straight line for each sample, and using the indicated line, the interpolated strength value was determined for each sample at a density of 44 lbs / cc. foot. In addition to determining MOR, the samples were then cut into 1 inch x 1 inch squares. The squares were glued face to the metal test fixtures, which made it possible to separate the samples by stretching them along the z axis, and thus determine the strength of the internal adhesive joint (IB). This test is widely used in industry. Maximum IB values are in psi. inch. The results are shown in table.13. The experiment was completely repeated a second time, the results are also shown.

Table 13 Description
(example 38) Unadjusted MOR value MOR for a density of 44 psi foot IB average pH glue Adhesive viscosity 1) Control, without DRO 1897 1711 114 4.19 3079 2) Dorus R-400 (5 2087 2014 131 4.28 2999 parts) were added to glue 3) First sprayed Dorus R-400 (5 2053 1919 145 parts), then sprayed D40999 / D41080 Repeat 1 2036 1892 101 4.3 2879 Repeat 2 2226 2063 139 4.3 3339 Repeat 3 2396 2157 140

When GDI is added to the adhesive based on PAE / soy, the MOR and IB values are significantly increased. Unadjusted MOR values were obtained by averaging the test results of 8 pieces for each sample. The IB results were the average of 6 pieces for each sample. When the experiment was repeated, similar results were obtained. A similar trend in MOR was observed, regardless of the application of the uncorrected MOR value or the MOR value interpolated to a board density of 44 lbs / cc. foot.

Preliminary spraying of HDI onto wood prior to spraying glue leads to an increase in MOR and IB compared to a sample without HDI. The increase is approximately equal to the increase achieved by adding HDI to the adhesive.

Claims (10)

1. An adhesive composition comprising soy, an amine-epichlorohydrin (AE) adduct and an isocyanate, wherein the AE adduct includes a polyamidoamine-epichlorohydrin polymer (PAE); the isocyanate includes poly (hexamethylene diisocyanate) (pGDI) or poly (methylene diphenyl diisocyanate); the ratio of the dry weight of the adduct AE / dry weight of the isocyanate is from 10: 1 to 1: 1 and the ratio of soybean / total content of the component of the adduct AE and the isocyanate component in the composition is from 1: 2 to 10: 1. 2. The composition of claim 1, wherein the isocyanate comprises a water dispersible isocyanate. 3. The composition of claim 1, wherein the AE adduct comprises a polyamidoamine-epichlorohydrin (PAE) polymer, the isocyanate comprises a water-dispersible isocyanate derived from poly (hexamethylene diisocyanate) (pGDI) or poly (methylenediphenyldiisocyanate), and the dry weight ratio of the adheat mass AE adduct isocyanate material is from 10: 1 to 1: 1. 4. The composition of claim 1, wherein the AE adduct comprises a polyamidoamine-epichlorohydrin (PAE) polymer, the isocyanate comprises a water-dispersible isocyanate derived from poly (hexamethylene diisocyanate) (pGDI), the protein source includes soy flour, and the dry weight ratio of the AE / dry adduct the mass of isocyanate is from 10: 1 to 1: 1. 5. Lignocellulosic composite comprising a composition according to claim 1 and a lignocellulosic substrate. 6. The composite of claim 5, wherein the protein comprises soy, the AE adduct comprises a polymer, polyamidoamine-epichlorohydrin (PAE), and the isocyanate comprises a water-dispersible isocyanate. 7. A method of obtaining a composite, which consists in the following stages:
a) obtaining a lignocellulosic substrate,
b) applying the adhesive composition according to claim 1 on a substrate and
C) maintaining the combination of the substrate / adhesive when heated and under pressure, while receiving a composite. 8. The method of claim 7, wherein the protein comprises soy, the AE adduct comprises a polyamidoamine-epichlorohydrin (PAE) polymer, and the isocyanate comprises a water-dispersible isocyanate. 9. A method of obtaining a composite, which consists in the fact that:
a) get lignocellulosic substrate,
b) apply isocyanate to the substrate,
c) a mixture of the adduct AE and soy is applied to the substrate, where the dry weight ratio of the adduct AE / dry weight of the isocyanate is from 10: 1 to 1: 1 and the ratio of soy / total content of the component of the adduct AE and the isocyanate component in the composition is from 1: 2 to 10: 1; and
g) maintain the combination of the substrate / adhesive when heated and under pressure, while receiving a composite. 10. The method of claim 9, wherein the protein comprises soy, the AE adduct comprises a polyamidoamine-epichlorohydrin (PAE) polymer, and the isocyanate comprises a water-dispersible isocyanate.