Stable adhesives from urea-denatured soya flour

FIELD: chemistry.

SUBSTANCE: method involves denaturing soya flour which basically involves thermal treatment of the soya flour in an aqueous solution, and then adding urea to the denatured soya flour which is essentially free from urease. The soya flour is denatured by heating to temperature 40°C-100°C for at least 15-500 minutes. The method also involves adding a cross-linking agent to the mixture of soya flour and urea and/or adding an emulsified or dispersed polymer. The polymer is selected from polyvinyl acetate or phenol-formaldehyde dispersions. The adhesives demonstrate high stability and adhesion-strength properties.

EFFECT: high adhesion strength in wet or dry state, with high efficiency of production and low production costs.

33 cl, 18 ex, 25 tbl, 22 dwg

The technical field to which the invention relates.

The invention generally relates to a method for production of stable products based on soy/urea (SUP) and to stable products based on soy/urea containing buried or emulsified polymers (SUPD) of urea denatured soy flour.

The level of technology

The adhesives on the basis of protein-containing soy flour were first widely used in the 1920s (US patents 1813387, 1724695 and 1994050). Soy flour suitable for use in adhesives, received and still receive by removing some or most of the oil from soybeans with the release of residual soy flour, which is then milled into flour very fine grinding. In typical cases, for extracting the most part, non-polar oils from crushed soybeans used hexane, although the methods of extrusion/extraction also suitable for removal of oil.

Received soy flour was then subjected to denaturation (i.e. change in secondary, tertiary and/or Quaternary structure of proteins with the release of additional polar functional groups capable of forming bonds) alkaline agent and to some extent hydrolysis (with the destruction of covalent bonds) with the release of adhesives for bonding wood in dry conditions. However, these first ADH is the Ziva soy-based prior art had a low resistance, and their use was strictly limited to work on the interior design.

In addition, the adhesives soy-based had a limited shelf life, and it was not possible to make them for the future. After only a few hours the viscosity and performance properties of the mixture of soy flour, denatured with alkali, quickly deteriorate (see figure 1). This deterioration is assumed to be the result of some hydrolysis of soy flour and excessive destruction of secondary, tertiary and Quaternary structures, which are supposed to play an important role in the formation of strong adhesive and cohesive ties. Thus, the balance between denaturation and save some secondary/tertiary/Quaternary structures has, apparently, essential for operational properties of adhesives.

In the 1920s, were first developed phenol-formaldehyde (PF) and urea (UF) adhesive resin. These phenol-formaldehyde and modified urea resin showed the durability in the work on the exterior, but the high cost of raw materials for their production initially resisted their use. The second world war has contributed to a rapid development of adhesives for use in the works, requiring them waterproof and pogolosovali, the wrench work on the exterior. However, the adhesives on a protein basis, mainly adhesives soy-based, continued to be used and in many works on interior decoration.

Emulsion polymers were also used as conventional adhesives. Emulsion polymerization is used to produce high-volume polymers, such as polyvinyl acetate (PVA), polychloroprene (PC), various acrylates and many resins based on copolymers of styrene-butadiene-Acrylonitrile. Emulsion polymerization is also used for the polymerization of methyl methacrylate, vinyl chloride, vinylidene chloride with styrene. In the last decade again showed interest in combining the above emulsion polymer adhesives soy-based, due to the low cost of such adhesives, and the need for adhesives that do not contain formaldehyde, for interior finishing. Currently using urea resins are produced mainly plywood, fibreboard medium density (MDF) and chipboard (PB). Although these resins show high adhesion with the substrate or adhesive strength, quick otverzhdajutsja and useful, they do not possess hydrolytic stability around the polymer skeleton. This is because the first selection of a large number of free formaldehyde from the finished product (and ultimately, inhaling his living in the house of the people). Adopted a number of legislative acts on the prohibition of the use of such resins in the interior design (California Air Resource Board-CARB, 2007).

As a source of raw materials for adhesives soy-based can be used soy flour, soy protein concentrates (SPC) and soy protein isolates (SPI). In order to simplify the present description, all soy products, containing more than 20% of the carbohydrates are indicated by the term "soy flour". Soy flour is cheaper than SPI, but it often contains high levels of activated urease (an enzyme that breaks down urea to ammonia), and therefore requires processing (denaturation) for the destruction of urease without violating the ratio of the viscosity/solids contents without impairing the finished product. Soy flour contains high levels of carbohydrates, which requires more sophisticated techniques of knitting (being sewn, these carbohydrates are able to greatly improve the resistance of the adhesives soy-based).

Carbohydrates are present in the soy flour in the form of both water-soluble and water-insoluble fractions. Of insoluble carbohydrates is mainly hemicellulose, along with a small amount of pulp. Soluble fraction consists mainly of sucrose, raffinose and Tahiti. Heat treatment of soy flour can trigger many reactions between carbohydrates and protein. These reactions are different in nature and are frequently referred to collectively as the Maillard reaction.

SPC contains a higher amount of protein than soybean meal, but lower than SPI. In normal cases, the SPC is obtained by washing with alcohol to remove soluble carbohydrates.

SPI is usually produced by the method of isoelectric precipitation. This method allows to remove not only soluble sugar and soluble low molecular weight proteins, leaving mainly of high molecular weight proteins that are optimal for bonding, even without modification. Due to this SPI gives a very strong adhesive with acceptable durability.

Disclosure of inventions

The present invention provides a method for the production of stable adhesives with improved adhesive strength in wet and dry condition. The method includes a heat treatment of soy flour to obtain denatured soy flour, does not contain, in the main, urease activity, and the subsequent addition of urea denatured soy flour with the formation of a stable adhesive based on soy flour, which is hereinafter referred to as product based on soy/urea (SUP).

"Stable" refers to an adhesive that remains is cabelino viscous and pH-stable over a, at least a few months. Under "pH stable" means an adhesive whose viscosity measurements by a rotary viscometer Brookfield (Brookfield) remains at the level of 500 centipoise for at least 20 hours. "Not containing primarily in the context of the description means that traditional tests do not detect the presence of soy flour significant amounts of urease, which in typical cases is measured by changes in pH over time. So, soya flour, "does not contain, basically," urease activity, shows the change in pH is less than one pH unit within thirty days in the presence of urea at room temperature.

Denaturation caused by heating soy flour to a temperature of at least 40°C to 100°C for at least 15 to 500 rpm, denatured soy flour contains at least 20% carbohydrates.

Urea is added to the denatured soy flour at a temperature of soy flour within the above range, preferably in an amount of up to five parts of urea per part of soy flour to a minimum of 0.25 parts of urea per part of soy flour. In one variation of the embodiment of the invention one part of urea is added to one part soy flour, while in an alternative embodiment, two parts of urea are added to one part seavoyage with obtaining a stable product based on soy/urea (SUP).

The method of the present invention also includes adding to the SUP cross-linking agent. A crosslinking agent may be do not contain formaldehyde cross-linking agent selected from polymeric methylene-diphenyl-diisocyanate (pMDI), aminopyrrolidine adduct, epoxy, aldehyde or mcevisualaid resin and combinations thereof. A crosslinking agent can also be not containing formaldehyde cross-linking agent selected from formaldehyde, phenolformaldehyde, modelinformation, melamineformaldehyde, phenolresorcin and any combination of these. A crosslinking agent is preferably added in the amount of at least 0.1% to 80 wt.% However, it can also be added and SUP at low levels in order to reduce the cost of traditional adhesives.

The method of the present invention also includes the addition of diluent to SUP. The diluent may be reactive or directionspanel and is selected from glycerol, ethylene glycol, propylene glycol, neopentyl glycol and polymer options. the pH of the finished adhesive can be adjusted by adding, respectively, the traditional acid or base.

The present invention also provides a method of preparing a stable aqueous dispersion or emulsion adhesive resin by adding to SUP emulsified or di is piergiovanni the polymer with formation of a stable dispersion or emulsion based product urea/soybean (SUPD). The method involves heat treatment of soy flour to obtain denatured soy flour, does not contain, in the main, urease; adding urea to obtain SUP and then combining the latter with emulsified or dispersed polymer with formation of a stable dispersion or emulsion of the product based on soy/urea (SUPD).

Denaturation is carried out by heating soy flour, which contains at least 20% carbohydrates, to a temperature at least 40°C to 100°C for at least 15 to 500 minutes

In one variation of the embodiment of the invention, the urea is added to the denatured soy flour at a temperature of soy flour from 40°C to 100°C., the Urea is added to the denatured soy flour in an amount equivalent to up to five parts of urea per part of soy flour to a minimum of 0.25 parts of urea per part of soy flour, education SUP.

SUP is added to the emulsified or dispersed polymers with access SUPD. Emulsion or dispersion of any polymer, including dispersion of polyvinyl acetate (PVA) or phenolformaldehyde (PFD), can be modified by adding the SUP of the present invention.

The method may also include adding a crosslinking agent to SUPD the present invention. A crosslinking agent may be do not contain formaldehyde Stivali the agent, choose from a polymeric methylene-diphenyl-diisocyanate (pMDI), aminopyrrolidine adducts, epoxy, aldehyde or mcevisualaid resin and any combination of these. A crosslinking agent may also be not containing formaldehyde cross-linking agent selected from formaldehyde, phenolformaldehyde, modelinformation, melamineformaldehyde, phenolresorcin and any combination of these. A crosslinking agent is preferably added in the amount of at least 0.1% to 80 wt.%.

The method of the present invention may also include additional stage spray or freeze drying to obtain a powdery adhesive.

The patent application U.S. No. 2004-0089418, claimed Li et al. (Li), describes soy protein, made with politicalintelligence resin (PARADISE). Li describes these specific PARADISE that is known as having a high adhesive strength when wet additives for paper and wood, in many possible reactions with the functional groups of proteins. According to Li, the denaturation of the SPI is carried out with alkali at the temperature of heating, and then denatured SPI is combined with the corresponding PARADISE-resin with the release of waterproof adhesive material. This water-soybean solution should be prepared immediately prior to copolymerization (and is, and subjecting the freeze-drying process) to achieve the required stability in storage. In the present invention, the modification of soy flour (containing both protein and carbohydrates) by the addition of urea leads to a completely unexpected increase in stability and a much more improved compatibility with comparable ratios soy/PAE without any noticeable reduction in the adhesion strength utverzhdenii resin in a dry or wet state.

Next, Li says nothing about the use of carbohydrates of soybean with PARADISE. Li talks about using SPI, which makes the process of denaturation is less relevant, because the protein has been intensive heat treatment. In contrast, traditional soy flour baking quality does not have an acceptable level of adhesion, if not to provide a stage of denaturation and the use of a crosslinking agent. Li says nothing about it.

Patent US 6497760 issued by Sun et al. (Sun), uses SPI as a starting material for the production of adhesives. Sun indicates the possibility of modification of soy flour, but not with urea. Urea is known as denaturing agent for adhesives with urease activity level from negligible to nonexistent, such as SPI. However, nothing is known that urea can serve as an effective denaturing agent for soy flour containing urease activity at the level of died authorized to high. While it is known that for denaturation SPI you can use urea (Kinsella, J. Am. Oil Chem. Soc., March 1979, 56: 244), Sun says nothing about the use of urea with soy flour in connection with urease activity. However, the present invention demonstrates, in fact, the application of urea as a particularly effective agent for denaturation and solvation soy flour, and in ordinary cases, the urea is added to the soy flour in small numbers and at higher temperatures than in the prior art.

In the present invention, urea is used for solvation and denaturation of soy protein, which makes the required functional groups it more accessible for adhesion and crosslinking. Cross-linking agents, such as AE and PAE (more broadly referred to as aminopyrrolidine adducts and polyaminoguanidine adducts), polyisocyanates, epoxy resins and formaldehyde resins, are commonly used today in the prior art. However, stable denatured by urea product based on soy flour (SUP) of the present invention also has improved compatibility with the substrate and stability when adding or without adding a suitable cross-linking agent, and a much higher resistance to biological attack.

The fact is Cesky all stable adhesive products on the basis of urea denatured soy flour (SUP) of the present invention showed increased resistance to biological attack within, at least a few months, which is very unexpected for soy protein in an aqueous environment. In addition, this distinctive characteristic is not dependent on the type of soy flour. All types of soy flour, be it soy flour with a high or low index of distribution of protein (PDI) or flour with high or low protein content showed the same effect up until urease activity was not significantly decreased.

Improved methods provide several advantages over prior art. First, SUP/SUPD of the present invention have a much lower viscosity than other adhesives soy-based, making it easy to carry and apply them. Secondly, SUP/SUPD of the present invention have a much higher resistance to biological degradation. Thirdly, SUP/SUPD of the present invention have a much higher percentage of solids. Fourth, SUP/SUPD the present invention exhibit higher reactivity with respect to certain cross-linking agents, showing excellent stability in storage in the presence of crosslinking agents. And finally, SUP/SUPD show excellent biological stability without the addition of biocides.

Brief description of figures

Figure 1 shows the profile of denaturation of soy flour using NaOH.

Figure 2 shows the pH-stabilin the industry products based on soy/urea in time.

Figure 3 shows the stability of the viscosity products based on soy/urea in time.

Figure 4 shows the stability of the viscosity products based on soy/urea (1:1) with 5% and 20% RYE in time.

Figure 5 shows the rate of increase of the adhesive strength (in dimensions using ABES = an automated system to evaluate the adhesion strength) of the products (pH 4.5) on the soy/urea (1:1) with 5% and 20% RYE in time.

6 shows the rate of increase of the adhesion strength (ABES) products (pH 7.0) on the soy/urea (1:1) with 5% and 20% RYE in time.

Fig.7 shows the rate of increase of the adhesion strength (ABES) products (pH 10,0) on the soy/urea (1:1) with 5% and 20% RYE in time.

Fig shows the rate of increase of the adhesion strength (ABES) products (pH of 4.7 and 7.0) on the soy/urea (1:1) with 5% RYE in time.

Fig.9 shows the adhesion strength (ABES/Instron = testing machine to evaluate the adhesion strength of the gap) products based on soy/urea/PARADISE in dry and wet conditions.

Figure 10 shows the preservation of the adhesion strength (ABES/Instron) in the wet state.

11 shows the rate of increase of the adhesion strength (ABES) products (pH 7.0) on the soy/urea (1:1) with pMDI in time.

Fig compares the rate of increase of the adhesion strength (ABES) adding 20% pMDI and HEAVEN.

Fig pokazyvayuschaya adhesion strength (ABES/Instron) in the wet state when adding 5% RYE soya products with different protein content.

Fig shows the stability of the viscosity and pH of the resins of the PVA/soy/urea.

Fig shows the adhesive strength under shear (ABES/Instron) resins from PVA/soy/urea in dry/wet condition.

Fig shows the adhesive strength under shear (ABES/Instron) resins from PVA/soy/urea (normalized to the content of solids in the dry/wet state.

Fig shows the adhesive strength under shear (ABES/Instron) resins from PVA/soy/urea (with low content of soybean urease) in dry/wet condition.

Fig shows the adhesive strength under shear (ABES/Instron) resins from PVA/soy/urea (all resins contain 75% PVA) in dry/wet condition.

Fig shows the adhesive strength under shear (wet/dry) resins from PVA/soy/urea 3-ply plywood panels hot pressing (maple).

Fig shows the adhesive strength under shear (wet/dry) resins from PVA/soy/urea 3-ply plywood panels of cold pressing (maple).

Fig shows the adhesive strength under shear (ABES/Instron) resins from PVA/soy/urea (dry/wet), modified crosslinking agent (all resins contain 75% PVA).

Fig shows the results of the analysis (ABES/Instron) dispersions soy/urea/PF.

The implementation of the invention

Soy flour after properly conducted its denaturation can serve as the excellent adhesive. In the process of denaturing the proteins in the soy flour, "deploy" their native structure, which makes available a large number of hydrophilic amide groups of the protein cage. Regulation of the degree of denaturation is critical in the production of adhesive with high adhesive strength and stability.

If the subject of soy flour in water solution heat treatment at a temperature of at least 40°C to 100°C for a period of time, at least from 15 to 500 minutes, you can get the solution of soya flour, denatured by heating and not containing mainly due to the large amount of urease. In one variation of the embodiment of the invention heat treatment of soy flour with a high content of urease is held at 90°C for 60 minutes, while soy flour with low content of urease - at 50°C for 60 minutes. While heat treatment of soy flour to the state denaturation is absolutely necessary, the exposure time at high temperature required to denature soy flour, depends on the required degree of denaturation and/or modification. The time required for denaturation of soy flour, also depends on the type selected (if required) cross-linking agent to provide additional water resistance.

Unfortunately, denatured by heating soy is the uke has a very high viscosity and has a low content of solids, which makes it difficult to transport and store, and begins to decompose or deteriorate" after only a few hours. However, the addition of urea denatured by heating and not containing mainly urease soy flour to obtain a stable product based on soy/urea (SUP) not only reduces the viscosity, but also (unexpectedly!) significantly increases the biological stability of the water product. In addition, the stability of the viscosity and pH products SUP far superior to traditional soy adhesives, even in the case of adding a cross-linking agent. Adding urea is critical in terms of viscosity control, compatibility with the substrate, stability and solvation (which increases the reactivity with respect to the corresponding cross-linking agents) adhesive, but it can only add the flour, previously subjected to denaturation by heating to reduce urease activity.

The urea concentration can be adjusted to control the flow characteristics or the glass transition temperature (T_gready adhesive resin. This allows you to expose SUP or SUPD spray drying and to transform the adhesive resin in the ready-to-use powder. In addition, the introduction of urea unexpectedly provides improved biological stability and stability to the to viscosity, and pH even when combined with certain cross-linking agents. Biological stability refers to the absence of growth of mould and/or the absence of decomposition, leading to the obtaining of the product with the smell of corruption.

In typical cases, the urea is made in denatured by heating and not containing mainly urease soy flour at temperatures from 40°C to 100°C. In one variation of the embodiment of the invention in the flour with a high content of urease urea is added at temperatures from 75°C to 90°C, while in the flour with a low content of urease - at temperatures from 45°C to 55°C. To obtain SUP takes about 15 to 500 minutes

Urea can serve several purposes in these products, including solvation, chemical reactivity, denaturation and biological stability. The degree of participation in each of these properties is unknown, but in all probability it at different levels add participates in all four. The amount of urea added to the denatured by heating the soy flour may be from about five parts of urea per part of soy flour (s/s) up to 0.25 parts of urea per part of soy flour (s/s); most preferably from two parts of urea per part of soy flour to about 0.5 parts of urea per part of soy flour. The level of urea can reg is encoded to control the characteristics of fluidity, or T_gthat adhesive that allows users to enter in this technology stage spray/freeze drying and turn the adhesive is a ready to use powder.

Adding urea at high temperatures allows the mixing of low viscosity, and also allows the urea to react with the components of soy flour, allowing, for example, carbamylcholine protein soy flour (Stark G.R. et al., J. Biological Chemistry 235 (II): 3177-3181 Nov. 1960). When you use soy flour with low levels of urease activity method can be simplified to the one in which urea and soybean mixed at room temperature, and then the resulting mixture is subjected to heat treatment in the desired temperature range. However, the flour with higher protein levels and elevated levels of urease activity has improved adhesive properties.

In some cases, it may be desirable to add a diluent or caustic agent to provide viscosity, stickiness or some other useful properties depending on the destination and/or use of a crosslinking agent. However, adding too much caustic agent in the adhesive can destroy residual tertiary/Quaternary structure of soy protein and rapidly lead to the release of ammonia, and in the context of cnom the end, to the deterioration of the performance properties of the adhesive. the pH of such adhesives is preferably less than 10, and in one variation of the embodiment of the invention the pH is from 5 to 10 for optimum stability and compatibility with the substrate. However, in some SUPD-systems pH can be less than 5.

SUP of the present invention may be added to the emulsified or dispersed polymers, for example, in the emulsion of polyvinyl acetate (PVA) and dispersion of phenolformaldehyde (PFD), to obtain a stable SUPD. In typical cases, adding not modified soy flour or NaOH-denatured soy flour directly to the emulsified polymers results in resins with a low stability, and compatibility with the substrate.

Adding the SUP of the present invention to emulsified or dispersed polymers is carried out by simple mixing of different, commercially available mixing tanks, tanks thinners or reactors. The temperature of the mixture is not considered a critical parameter, and is typically used at room temperature, although it may be desirable and acceptable combination SUP with emulsified or dispersed polymer at elevated temperatures. For optimal stability SUPD may require adjustment to the final pH with acids or bases, however, such regulation is usually pretty reasonable and is more suitable to ensure the stability of the emulsion or dispersion than the component based on the soy/urea.

SUP or SUPD the present invention can be used in its native form, or may be modified further by the addition of an appropriate cross-linking agent(s). The type and amount of crosslinking agent may depend on the amount of carbohydrates in soy flour. For example, the amount of carbohydrates in the flour can vary from 1% to 60% depending on pre-treatment of soy flour. Some types of flour, i.e. soy protein concentrates (SPC), in typical cases contain from 15% to 30% carbohydrates, while other types of soy flour can contain from 40% to 50% carbohydrates. In one variation of the embodiment of the invention the soy flour contains 20% carbohydrates. Since carbohydrates are the main cause of low water resistance of soy flour, stitching these carbohydrates allows you to get the adhesive with high adhesive strength (dry and wet). In addition, the stitching of carbohydrates leads to the production of adhesives with low water-absorbing capacity and the ability to swell (which may cause adhesion of adhesives in the wet state).

A crosslinking agent may contain or not contain formalize the ID. While for the interior works more desirable cross-linking agents that do not contain formaldehyde, with some work on the exterior finish is also good and formaldehydefree cross-linking agents. Does not contain formaldehyde cross-linking agents suitable for use with adhesives of the present invention include isocyanates such as polymeric methylene-diphenyl-diisocyanate (pMDI), aminopyrrolidine resin, epoxy, aldehyde or mcevisualaid resin capable of reacting with soy flour. Under aminopyrrolidine resins are resins obtained by the reaction of epichlorohydrin with amidofunctional compounds, among which are politicalintelligence resin (PAE resin), polyalkyleneglycol resin (RARE-resin) and aminopropionitrile resin (Aer-resin). PARADISE-resin include apatityvodokanala PARADISE-resin-based secondary amines, such as Kymene™ 557H, Kymene™ 557LX, Kymene™ 617, Kymene™ 624 and ChemVisions™ CA1000 (all from Hercules Incorporated, Wilmington DE); epoxy-functional resin on the basis of tertiary amine-polyamide and epoxy-functional PARADISE-resin-based tertiary amine-polyamidoamine, such as Kymene™ 450 from Hercules Incorporated, Wilmington DE. Suitable for stitching RARE-resin is Kymene™ 736 from Hercules Incorporated, Wilmington DE. Kymene™ 2064 is APE-resin from Hercules Inorporated, Wilmington DE. They are widely used industrial materials. Their chemistry is described in the following link: N.N. Espy, "Alkaline-Curing Polymeric Amine-Epichlorohydrin Resins", in Wet Strength Resins and Their Application, L.L.Chan, Ed., TAPPI Press, Atlanta GA, pp.13-44 (1994). You can also use low-molecular aminopyrrolidine condensates, such as described by Coscia (patent US 3494775), as not containing formaldehyde cross-linking agents. Possible formaldehydefree crosslinking agents include formaldehyde, phenolformaldehyde, modelinformation, melamineformaldehyde, finalreports and any combination thereof.

The role of cross-linking agent, regardless of its type, is to increase the density of crosslinking in the adhesive, the increase in Tg with decreasing solubility with greater adhesive strength in dry and wet conditions. This is best achieved by using cross-linking agents, in a molecule with multiple reactive sites. For example, in one variation of the embodiment of the invention, cross-linking agents that do not contain formaldehyde, include PARADISE in amounts from 0.1% to 80%, and formaldehydefree cross-linking agents include phenolformaldehyde in amounts from 1% to 90%.

A crosslinking agent is typically added to SUP or SUPD prior to application of the adhesive to the substrate, but in nectariniidae it may be added for a few days or even weeks before use of the adhesive. The stability in storage of the finished adhesive depends on the modes denaturation, and the type and amount of crosslinking agent, but may be more than a few days. Thus, using the method of the present invention achieves a significant increase compared to denaturirovannyj alkali products (see figure 1), the stability of the viscosity. For example, traditional, denatured with alkali adhesives usually are suitable for use only within a few hours, even without adding a crosslinking agent that owing to the excessive denaturation and/or destructive hydrolysis accompanied by a rapid loss of tertiary/Quaternary protein structure, which is particularly important for obtaining protein adhesive with good adhesive strength.

In addition to the crosslinking agent, SUP/SUPD-adhesives of the present invention may be a number of reactive or directionspublic thinners. These diluents can be used to improve the solvation, followed by denaturation or any other modification of the physical properties of the adhesive on the soy/urea. Possible to use solvents include polyols, such as glycerin, ethylene glycol, propylene glycol or other suitable for this purpose hydroxyl-containing monomer or polymer material, defoamers, humectants and the RV, typically used in the prior art. These solvents/additives can be introduced at levels from 0.1% to more than 70% of the total mass of the adhesive. These thinners/modifiers can be entered at any stage of the method, i.e. before, during or after the stage of inaktivirovanie urease heat.

The adhesive of the present invention can be applied to a suitable substrate in amounts from 1% to 25 wt.%, preferably from 1% to 10 wt.%, most preferably from 2% to 8 wt.%. Some examples of suitable substrates include (but their list is not limited named here) lignocellulosic material, wood or fiberglass. The adhesive can be applied by any means known from the prior art, including drawing roller, knife, extrusion, irrigation, devices for applying foam or by spraying, such as a resin applicator with a rotating disk.

The use of adhesives in the manufacture of lignocellulosic composites described in the "Wood-based Composite Products and Panel Products", Chapter 10 of Wood Handbook - Wood as an Engineering Material, Gen. Tech. Rep. FPL-GTR-113, 463 pages, U.S. Department of Agriculture, Forest Service, Forest Products Laboratory, Madison, WI (1999). A number of materials, including chipboard, oriented strand Board (OSB), wood particle Board, wafer type, fibre boards (including fibreboard medium platnosci high density), material from a flat wood strands oriented in one direction (PSL), laminated material made of glued wood chips (LSL) and other similar materials. Lignocellulosic materials such as wood, wood pulp, straw (including rice, wheat or barley straw), flax tow, hemp cake and bagasse sugar beet or cane (bagasse), can be used in the production of thermoset products of the invention. Lignocellulosic product is typically manufactured by mixing the adhesive with the substrate in the form of powder, particles, fibers, chips, flocculent fibers, wafers, scrap, shavings, sawdust, straw, ó or stubble and subsequent pressing and heat treatment of the mixture before formation of the curable material. The moisture content of lignocellulosic material before mixing with the adhesive composition should be in the range from 2% to 20%. The adhesive compositions can also be used for the production of plywood or laminated veneer from veneer lumber (LVL). The adhesive composition may be applied to the surface of the veneer using a roller, scraper, by irrigation or spraying. Then many layers of veneer superimposed on each other with the formation of the panel thickness. The panels are placed in a hot press (for example, with a heated stove) and Pres is described to full adhesion and curing of the materials in the beam. Fibrobeton can be produced by means of wet skolachivaniya (felt making)/wet pressing, dry skolachivaniya/dry pressing or wet skolachivaniya/wet pressing.

Along with lignocellulosic substrates, the adhesive can be used with such substrates as glass wool, glass fiber and other inorganic materials. The adhesive of the present invention can also be used with combinations of lignocellulosic and inorganic substrates.

To assess the following characteristics of the adhesives on the basis of soya flour/urea.

(1) Physical properties: basic characteristics, which are taken into account, is the viscosity, measured by a rotary viscometer Brookfield model LVT, two speeds of rotation 30 and 60 rpm, 4 spindle (1-4), which were selected taking into account the viscosity of the product, the solids content after aging in an oven (stove) (150°C/1 h or 125°C/1.5 h), which led to some loss of free urea, which explains why theoretical values are higher than measured values); the pH value viscosity at room temperature and biological stability was determined by visual observation for signs of decay or damage like soy milk).

2) the slew Rate of the adhesion strength in the dry state: adhesion what I shear strength of two laminated veneer layers was evaluated using the Automated Bonding Evaluation System (ABES) is an Automated system for evaluating the adhesion strength) AES, Inc. This system was used to determine how increased over time, the adhesive strength of the adhesive with the substrate under certain temperature and time regimes pressing. All of the examples were used, the temperature of the pressing 120°C. the evaluation was based graph slew rate relative adhesion strength of different adhesives as a function of time of pressing. Sample preparation was carried out according to the method of determining the adhesion strength in shear/break using HRT ABES/Instron, but their trials were carried out in the device ABES within a few seconds after pressing.

3) Save the adhesion strength in the wet state: insufficient adhesive strength in the wet state can occur if the line gluing (glue line) cannot correct the distribution of stresses at the interface of the wood/adhesive, due to the expansion/compression of the wood during the process of wetting and drying. Save the adhesion strength in the wet state is calculated as % residual adhesion strength in a dry condition after soaking.

4) Assessment of plywood for interior design: samples of 3-ply plywood manufactured from veneers of douglasii (lieshi fiscaliste, family coniferous) method, described below, and subjected who were tested according to the standard for interior plywood American Association plywood manufacturers ANSI/HPVA HP-1-2004 4.6 "Three-cycle Soak Test" (test with three cycles of soaking).

Determination of the adhesion strength by the method of HRT ABES/Instron

Manufacturing of samples: samples of wood were re-stamped veneer of Eastern white or Weymouth pine, using ABES-forming device so that the sizes of the prepared samples was 11.7 cm along the fibers and 2.0 cm perpendicular to the fibers, and a thickness of 0.08 to see the Test adhesive was applied to one end of the sample so that it completely covered superimposed on each other areas; the rate of application of the adhesive in most cases ranged from 3.8 to 4.2 mg/cm²wet weight. Then the sample was glued with the second veneer (the time of the open shutter of the adhesive layer was less than 15 seconds to ensure optimal transfer) and were placed in ABES device so that the area of calling each other plot glued samples was 1.0 cm × 2.0 to see If everything was going properly, all samples were merged for the 2.0 min at 120°C under pressure of 9.1 kg/cm². Then all glued samples were left alone for conditioning for at least 48 hours in a controlled atmosphere at a temperature of 22°C and relative humidity of 50%.

Evaluation of the adhesion strength: preparation of samples of each resin was carried out by the method described above. After conditioning tenth five of the samples were tested using an Instron machine at a speed of 1000 slider 10 mm/min The maximum load that causes the destruction of samples were recorded for each sample. These samples were designated as samples for evaluation of the adhesion strength in the dry state. The remaining five samples were placed in a water bath with a temperature of 22°C for four hours. Then, the samples were removed from the water bath and immediately tested as described above. These samples were designated as wet samples (to assess the adhesion strength in the wet state). To hold the thin samples inside the machine Instron were provided special grips. Obtained for each resin is represented the average of five tests samples, and fixed the error is the standard deviation. Typical coefficients of variation (COV) in this method amounted to about 15% when evaluating the adhesion strength both dry and wet condition, which can be seen as an excellent result in light of the variability of the indicators of the wood.

A method of manufacturing a 3-layer panels of veneer of douglasii

Prototyping: used veneer of douglasii size of 8 inches (20.32 cm) × 8 inches (20.32 cm) and a thickness of 1.6 inch (4,25 mm). Test the adhesive is first applied to one side of the Central veneer. Then top on this side of the superimposed upper veneer so that the fiber directions about what their veneers were perpendicular to each other. The time of the open shutter of a glutinous seam in this case was not provided. Thereafter, the adhesive was applied to the other side of the Central veneer, and lower veneer superimposed over this side of the Central veneer so that the fiber directions of both veneers were perpendicular to each other. Typical rates of consumption of adhesives ranged from 21.5 to 22.5 mg/cm²line gluing wet weight. Then glued the sandwich panel were merged for 5 minutes at 150°C under pressure of 11.0 kg/cm²after which the samples were left alone for conditioning at 26°C and relative humidity of 30%, for at least 48 hours prior to testing.

Testing of samples: the samples were tested according to ANSI/HPVA HP-1-2004 4.6 "Three-cycle Soak Test" (test with three cycles of soaking).

A method of manufacturing a 3-layer panels of veneer maple

Prototyping: used maple veneer size of 8 inches (20.32 cm) × 8 inches (20.32 cm) and a thickness of 1.6 inch (4,25 mm). Test the adhesive is first applied to one side of the Central veneer. Then top on this side of the Central veneer coated with adhesive overlaps the bottom of the veneer so that the fiber directions of both veneers were perpendicular to each other. The time of the open shutter of a glutinous seam in this case did not involve the ü. The obtained two-layer panel is then turned over so that the Central veneer on top. Thereafter, the adhesive was applied to the other side of the Central veneer and the top veneer superimposed over that side of the Central veneer so that the fiber directions of both veneers were perpendicular to each other. Typical rates of consumption of adhesives ranged from 21.5 to 22.5 mg/cm²line gluing wet weight. Then glued the sandwich panel were merged for 5 minutes at 150°C under pressure of 11.0 kg/cm²after which the samples were left alone for conditioning at 26°C and relative humidity of 30%, for at least 48 hours prior to testing.

Testing of samples: the samples were tested in accordance with ASTM D905 (standard of the American Association for testing materials).

Examples

The following examples disclose various aspects of the present invention. It goes without saying that these examples are provided only to illustrate the invention and in any case not be considered as limiting the scope of the invention. Raw materials in these examples was following.

Soy flour from ADM (Decatur, IL), grade IV, the moisture content of 4.7%, and roasted soybeans (CG4) from Cargill (Minneapolis, MN); soy protein concentrates (SPC) from ADM (AVF); soy protein isolates (SPI) "SPI rofam 974" from ADM; urea (commercial grade)purchased from Univar; RYE: "Chem Visions™ CA 1000 PARADISE" from Hercules, pH 2,62, the solids content after soaking in a drying oven at 150°C/1 hour=20,04%; pMDI: "PAPI™from Dow Chemical (Midland, MI); PVA: "DUR-A-FLEX™" from Franklin, Int. of (Columbus, OH); epoxy resin "ANCAREZ AR550" from Air Products Chemicals Inc. of Allentown, PA, and "Arolon 850-W-45" from Reichold of Bridgeport, NJ.

Example 1

Soy flour was subjected to denaturation by heating, and then the reaction with urea to obtain a stable water-based products soy/urea (SUP). The methods described in examples 1A and 1C, identical, differing only in the number of raw materials used. Example 1D is similar to example 1B, although used in these different temperature (D - 50°C, B - 90°C); in example D was also used roasted soybeans with low content of urease (CG4).

Method of preparation: in a three-neck round bottom flask with a heat-insulating jacket, temperature controller, reflux condenser and mechanical stirrer poured water. In water at room temperature was added soy flour over a period of time from 2 to 5 minutes and the Mixture was viesulas for 5 minutes until smooth, and then was heated to 90°C for 15 to 30 minutes the Reaction was conducted at 90°C±2°C for 1 hour under conditions of stirring, during which it released from urease soy flour was added to urea, and the reaction mixture was again brought to 90°C and vyderzhivala is at 90°C±2°C under conditions of stirring for 1 hour. Next, the reaction mixture was cooled to 25°C in a bath of ice water, and was stored until use in plastic bottles at room temperature.

Discussion: all the products of examples 1A-1D was a very homogeneous mixture. Physical properties are presented in table 4. As expected, the viscosity decreased significantly, and the solids content increased with increased levels of urea. Some of the increase in pH is out, presumably, the result of trace quantities of urease activity still present in the product and serving to cause the formation of ammonia, which raises the pH, but the ammonia smell was not felt in any of the samples, even after 3 months. Indicators of the stability of the pH and viscosity of the discussed products (respectively 2 and 3) clearly show that obtained at 90°C, the products have excellent stability and is suitable for the transportation of the traditional methods of pumping fluids. An interesting fact is that obtained at 50°C. the product was much more liquefied and showed lower stability of the pH and viscosity than obtained at 90°C analogue that is probably the result of incomplete denaturation or absence of a reaction between urea and soybean.

Moreover, the product of example 1D had no biological resistance of other resins and started to deteriorate" after less than 3 weeks, which is probably the result of low levels of urea, caused by the collapse of urease (draws attention to the marked difference between theoretical and the actual solids content and the presence of the ammonia smell). The behavior of the products during liquefaction under the action of the shift was often forced to doubt read from the device constant viscosity and is a likely cause of some of the forms, abudumah figure 3. This distinctive characteristic (dilution under the action of the shift) was observed in all containing soy protein water products, but yet he was weaker pronounced than in typical denaturirovannykh alkali products, and, in all probability, it can be regarded to some extent as a function of the total content of urea, which can facilitate the practical application of such products. The most important is that the products of examples 1A-1C was still liquid and resistant to biological degradation after more than 3 months of curing at room temperature. Ordinary denatured by heating soy flour (without urea at 90°C) gives not dense fluid products in concentrations less than 15% show a high degree of biological decay within 24 hours. Thus, it was unexpectedly found that urea can serve as the required biocide/preservative in these products.

Example 2: COMPARATIVE EXAMPLES

In some recent works have demonstrated the adhesion strength in dry and wet condition known adhesives from soy-protein isolates (SPI) without adding a crosslinking agent. Comparative evaluation of these adhesives with adhesives of the present invention showed the improvements that may be implemented using cheaper soy flour with a high carbohydrate content.

The product of example 2A was a denatured by urea at low temperature the product is manufactured according to the method of Sun (patent US 6497760, see above), except that the solids contents were 23.9 percent instead of 14.0%. In addition, the product according to Sun dried freeze-drying, and the product of the present invention was used immediately.

A method of manufacturing a water and urea was drained into a three-neck round bottom flask with a heat-insulating jacket, temperature controller, reflux condenser and mechanical stirrer. The solution was heated to 25°C and upon reaching the specified temperature in the continuation of 15 min was added SPI. The mixture was aged at 25°C±2°C for 1 hour under the conditions of mixing. The obtained reaction product was stored until use at room temperature.

The product of example 2B was a denatured with alkali, soy product made as described in example 1.3 of the way of the Sun. These products have served as an excellent samples for comparative examples according to the assessment requirements of the adhesion strength of the adhesive for production of plywood from veneer of douglasii designed for interior decoration, as these products have been able to pass the suitability test of plywood for interior decoration when applying them, contrary to tradition, on both sides of the veneer (ANSI/HPVA HP-1-2004 4.6 "Three-cycle Soak Test").

Method of manufacturing: in a three-neck round bottom flask with a heat-insulating jacket, temperature controller, clicks Tim fridge and a mechanical stirrer was flooded with water. Then added SPI within 2 to 5 minutes the Reaction was conducted under conditions of agitation for 30 min at 22°C. Then was added 50% NaOH, and the reaction mixture was heated to 50°C. the Mixture was aged at 50°C±2°C for 2 hours under stirring. The obtained reaction product was cooled to 25°C and stored until use.

Discussion: the physical characteristics of both products (examples 2A and 2B) are presented in table 7. These products were much more viscous than the products shown in table 4, when comparing the solids content. Most notable is the fact that the product of example 2A with a high content of urea was the same (25 times more viscous) viscous as the product of soy flour/urea (1:2) example; specified product of comparative example also showed low content of solids (23,9 against 35,0). This high viscosity at low solids contents was a big problem even in the case of the modified alkali product (example 2B). The method of the present invention gives products based on soy flour/urea, which are more viscous at high solids contents as compared with the resin-based SPI prior art. Compare products were tested with method HRT ABES/Instron, and the method of manufacturing a 3-layer panels of veneer of douglasii.

Soy flour/urea with added RYE: although the adhesives on the basis of soya flour/urea can be used in n is positive, water limited. To provide additional resistance to swelling in water and, consequently, to improve the adhesion strength in the wet state can be added a crosslinking agent. A crosslinking agent makes the products more density knitting.

Examples 3-5 illustrate cross-linking ability of a typical RYE-resin product based on soy flour/urea (1:1) (analogously to example 1B). To determine the effect of pH on the final performance properties and characteristics of a pure, without impurities, the product as the initial pH value of the mixture of soya flour/urea were selected following pH levels: 4,5; 7,0; and 10.0. Levels PARADISE 0.5% and 20% (s/s) were evaluated in terms of their impact on the stability and performance properties.

Example 3

Method of manufacturing: product made as described in example 1B, was placed in a three-neck round-bottom flask equipped with a mechanical stirrer. the pH was lowered by adding 50% H₂SO₄at room temperature under the conditions of mixing. After adding the acid solution was vynashivalsya for 15 min, and then stored until use at room temperature.

The product of example 3A was placed in a beaker and added with stirring to the desired number of PARADISE. The products of examples 3B and 3C were similar way the. Samples were intensively mixed for 1 min until complete homogeneity, and then stored until use at room temperature.

Example 4

The products of examples 4A-4C (0.5% and 20% RYE) was produced in the same way as the products of examples 3A-3C, but with a slightly higher initial pH of the raw product 1B. the pH of the product of example 4A was reduced only up to pH 7.0 by adding 50% H₂SO₄.

Example 5

The products of examples 5A-5C (0.5% and 20% RYE) was produced in the same way as the products of examples 3A-3C, but at higher initial pH of the raw product 1B. the pH of the product of example 5A was increased to a pH of 10.0 by adding 50% NaOH. Features 9 products obtained in examples 3-5, shown in tabl.

the pH of the finished product (after adding PARADISE) did not differ much from the initial pH of the product based on soy flour/urea, except for products with pH10. In the latter case, the pH was very sensitive to the addition of RYE. So, all the products with pH 10 immediately began to emit gas for the ammonia resulting from the alkaline reaction of disintegration. As such, the pH of the finished composition may change after adding PARADISE as a cross-linking agent.

All products tabl showed acceptable stability viscosity for at least 5 hours, and several products for more than 20 hours to more than 3 days. Figure 4 reflects the stability of the products of examples 4B and 4C. Adding 5% PARADISE (example 4) viscosity remained largely unchanged in the continuation of more than 24 hours, indicating the possibility of manufacturing a single component product. The initial decrease in viscosity observed in both products, is explained mainly by pricing at a scale that can reduce/eliminate by adding certain defoamers.

As the ultimate bond strength of the product and the slew rate of this strength are important to determine the commercial viability of any candidate on the adhesive. All products table was estimated according to the method of Estimating the rate of rise of adhesive strength described earlier in this application. The evaluation results are shown in figure 5-8. In all cases, there is a clear sequential increase is the limit of adhesion of adding RYE as a crosslinking agent, although the addition of 5% PARADISE actually provides a more significant increase compared to 0% PARADISE than 20% PARADISE compared to 5% PARADISE, suggesting the existence of an optimal level of introduction of PARADISE in the system.

Both types of samples with pH 7.0 and pH of 10.0 (examples 4 and 5) also showed a higher initial rate of increase of the adhesion strength as compared with the control resin with 0% PARADISE. However, in samples with a pH of 4.5, this phenomenon was not observed, probably due to slow reactions with PARADISE in the specified conditions. Also of interest is the fact that products with 5% PARADISE (example 3B) showed, as it turned out, slowed the rate of curing at pH 4.5. This may partly explain the low adhesive strength of such samples in the wet state compared with other samples (see Fig). To evaluate the adhesion strength in dry/wet condition 9 adhesives from table (3A-3C, 4A-4C and 5A-5C), as well as two products of the comparative examples (examples 2A-2B), the methodology developed HRT (HRT ABES/Instron).

Fig.9 shows the results of evaluating the adhesion strength under shear of all tested samples (2A-B, 3A-C, 4A-C, 5A-C) in a dry and wet state, and for ease of comparison, these results are presented in one line in chart form. Figure 10 shows the % save adhesion strength (100 the adhesive strength in the wet/dry). Compare SPI-products, in General, have clearly demonstrated that they have excellent adhesive strength in dry and wet conditions without the addition of crosslinking agents, which cannot be said about products based on soy flour/urea, which require the addition of a suitable cross-linking agent to achieve acceptable adhesion strength in dry and wet conditions.

However, the products made at pH 4.5, do not follow this trend. In fact, the maximum adhesive strength in the wet state at a pH of 4.5 was only observed in the product, containing 0% PARADISE. Adhesive strength in the wet state at the specified pH was increased with the addition of RYE, but not to the level that was observed in samples with higher pH. Except for the data at pH 4.5, the addition of 5% RYE increased adhesive strength in a dry condition, on average, 58%, and wet - on average 572%. Adding 20% RYE in products with pH 7.0 and pH 10.0 to increased adhesive strength in a dry condition at 97%, and wet - on "implausible" 952%.

If we compare the products of examples 2A and 4A, which both contain about 25% protein, calculated on the dry matter, the influence of carbohydrates on the strength properties of flour compared with isolates obviously in full. Adding 5% of a crosslinking agent in the sample 4B reduces, cos the main, the influence of carbohydrates due to the formation of less hygroscopic carbohydrate-protein polymers with higher molecular weight. Thus, the joining of carbohydrates is a key factor in making the adhesion strength of the soy flour in the wet state.

Example 6

In the present example was evaluated pMDI as a crosslinking agent for a product based on soy flour/urea (1:1). As in the examples from HEAVEN, we evaluated the inuence of the concentration of cross-linking agent. In this example, the initial pH of the product based on soy/urea (1:1) was 7.0 at levels pMDI 5% and 20%. A method of manufacturing products was identical to the method used in example 4.

Discussion: the use of pMDI as a crosslinking agent were evaluated by the same procedure which was used in the case modified by the addition of RYE products of example 4. Characteristics of products based on soy flour/urea/pMDI are given in table 14, the curves in the rate of increase of the adhesion strength - figure 11. In General, the viscosity products with pMDI was slightly lower (even at high solids contents)than their analogues, modified HEAVEN. Moreover, products with pMDI had weakly lower pH. The results of the evaluation of the rate of increase of the adhesion strength show that the adhesion strength in the dry state was increased as a function of the content of pMDI. In addition, the slew rate of the adhesion strength is also greatly increased with the introduction of cross-linking agent (similar to what was observed in the case of PARADISE-modified resins). The results of the direct comparison PARADISE-modified products with pMDI-modified products presented on Fig show that both products were quite comparable in the framework of the adhesion strength and almost identical in speed of its rise. The test results with soaking performed on the samples 3-ply is anery, suggest that urea may interfere with the reaction between pMDI and soy, so when using a pMDI as a cross-linking agent is preferable to apply a higher ratio of soy/urea.

Example 7

The criterion of quality plywood for interior decoration is the method of stratification in a moist condition, developed by ANSI (American Association of manufacturers of plywood). Although a wide range of products associated with this market, a large percentage of them made all of wood douglasii (lieshi fiscaliste). In the present example was evaluated several adhesives based on soy flour/urea, along with the adhesives of comparative example 2. Samples glued with adhesives based on soy flour/urea, produced in the manner described above for the production of sandwich panels of wood douglasii. Samples, glued products of examples 2A and 2B were made in another way (the way Sun): by applying 7.5 g of wet adhesive to one side of each of the upper and lower layer and on both sides of the Central layer. The time of the open shutter adhesive composition before applying the layers to each other so that the fiber direction of the Central layer was perpendicular to the direction of fibers of the upper and lower layers was 15 minutes. Then trechsel is ina panel was merged within 15 minutes at 104°C under pressure of 11.0 kg/cm ². All panels were tested according to ANSI/HPVA HP-1-2004 4.6 "Three-cycle Soak Test". The results are presented in tabl.

Example 8

Evaluated the effect of protein content on the stitching with the help of HEAVEN in order to show the importance of using carbohydrate-containing soy product. In this example, three different adhesive on the soy/urea (with different protein content) were prepared by the method described in example 1C. In all cases the ratio of the soy/urea was 1:2, and as a cross-linking agent was applied PARADISE in the amount of 5%, which was added in the same manner as described in example 4B. Characteristics manufactured adhesives are given in table 16. Adhesive strength in the wet state of each of these adhesives was evaluated by a previously described method ABES/Instron. The observed increase in the adhesion strength in the wet state compared with the resin without cross-linking agent represented graphically on Fig as a function of protein content. In addition, the adhesive 8D was subjected to soaking in the conditions described in example 7, and the sample passed the test with a minimum amount PARADISE (5%).

Discussion: the results Fig clearly show that the impact of PARADISE as a crosslinking agent was not reduced in the presence of carbohydrates, but actually increased. Probably this is the result, primarily, of those reactions PARADISE-a PARADISE that occur in such systems is Emax, that is confirmed by the indicators adhesive strength of adhesives on the basis of only PARADISE, presented in table 16. These results clearly show that the carbohydrate fraction is an important factor in the formation of resistance in adhesives based on soy flour.

Example 9

In some cases it may be desirable introduction directionspanel or reactive diluent to improve the adhesion strength in wet or dry products with or without added cross-linking agent. The samples were produced as described in example 3, except that the mixture was added glycerin in relation to soy in the product to 5%, 25% or 100%. The results of this study are presented in table 17.

Discussion: results in table 17 show that the adhesion strength in wet or dry condition can be improved dramatically by the addition of diluent. It is possible that this increase is due to a number of reasons, but most likely it is due to the improvement of solubility or stabilization of the secondary/tertiary structure, which is a key factor in maintaining the adhesion strength of soy adhesives or improved impregnation of the substrate. Although example 9 demonstrates the possibility of introducing a diluent/modifier after heat treatment, in some cases it may be acceptable or even preferred the introduction of diluent/modifier before the stage of inaktivirovanie urease.

The polyvinyl acetate (PVA) industrial production were used to assess the relative impact of adding resins based on soy/urea on the physical properties and performance characteristics of the panels. Table contains the evaluation results of the control samples.

In examples 10-20 soy flour was first subjected to denaturation by heating, and then the reaction with urea with the formation of a stable aqueous resin-based soy/urea. The method can be one - or two-stage.

In the first example were used with the one-stage method using a mixture shown in table 19.

Method of manufacturing: in a three-neck round the bottom flask with a heat-insulating jacket, a temperature controller, a reflux condenser and a mechanical stirrer was flooded with water. In water at room temperature was added urea, and the mixture is stirred over a period of time from 2 to 5 minutes to dissolve. Then quickly stir the solution was introduced soy flour (IV) continued 5 min at room temperature. The mixture was viesulas 5 minutes until smooth, and then was heated to 90°C for 15 to 30 minutes the Reaction was maintained at 90°C±2°C for 1 hour under stirring. The reaction mixture was cooled to 25°C in a bath of ice water, and was stored until use in plastic bottles at room temperature.

Example 11

This example demonstrates the two-stage method using soy flour with a high content of urease.

Method of manufacturing: in a three-neck round bottom flask with a heat-insulating jacket, temperature controller, reflux condenser and mechanical stirrer poured water. In water at room temperature was added soy flour (IV) for a period of time from 2 to 5 minutes and the Mixture was viesulas 5 min until homogeneous, and then was heated to 90°C for 15 to 30 minutes the Reaction was maintained at 90°C±2°C for 1 hour under conditions of stirring; at the same time added urea and the reaction mixture was again brought to 90°C and was maintained at 90°C±2°C under conditions of stirring for 1 hour. The reaction mixture was cooled to 25°C in a bath of ice water, and was stored until use in PLA is teak bottles at room temperature.

Examples 12-18

In examples 12 to 18 were used either single-stage or two-stage methods described respectively in examples 10 and 11. In these methods, used different ratios of soy/urea and the reaction temperature (see table 21, which shows detailed characteristics of these resins).

Examples of products based on soy/urea/PVA: to assess the ability of the adhesives on the basis of soy/urea to function as adhesives or fillers, cost-cutting cost) with polyvinyl acetate (PVA) were made several combinations of adhesives on the basis of soy/urea/PVA using the following method.

Method of manufacturing: PVA loaded into the three-neck round bottom flask equipped with a mechanical stirrer and thermometer. The temperature was set at 22°C-24°C using a water bath. In a rapidly stirred emulsion PVA at room temperature for 2 to 5 min was added with the adhesive of the soy/urea (selected from examples 10-18). The total mixture was mixed in the sequel to 15 minutes, until it is completely smooth. Measured pH of the mixture, which was designated as the "initial pH". For lowering the pH value to the end value of 4.4 to 4.6 was added dropwise sulfuric acid (50%). The amount of acid required to lower pH, calculated by concentrated sulfuric acid, calculated on the solution. Receiving the data adhesives based on PVA/soy/urea was vymeshivanii for an additional 15 min, and then it was stored until use in plastic bottles at room temperature.

Discussion: excellent stability, shown by adhesives on the basis of soy/urea was also observed among resins based on soy/urea/PVA (Fig). It is noteworthy that the pH-stability of the resins on the basis of the soy/urea/PVA was much higher than that of the control resin based on urea/PVA (example 3C). In addition, the adhesion strength when diluted under the action of shear, shown resins based on soy/urea, all of the resins on the basis of the soy/urea/PVA was reduced and sometimes absent.

Assessment of operational properties (method ABES/Instron): about PVA adhesive strength in the wet state in a typical PVA compositions, little is known. As shown in Fig, resin-based soy/urea also unsuitable for work in a humid atmosphere without the addition of a reactive cross-linking agent. However, from 25% to 50% PVA can be replaced with a resin-based soy/urea with minimal loss of adhesive strength in the dry state, even at low percent solids content.

On Fig presents chart indicators adhesion strength in shear dry or wet resin Fig, normalized to the solids content. From Fig can be seen that there is no any noticeable reduction in deionno strength of these resins is not observed, even when replacing PVA resin-based soy/urea up to 50%. Thus, the combination with PVA adhesive on the soy/urea at 50% of the same adhesive strength (with regard to the content of solids) PVA. It should be noted that samples with replacement of 50% PVA-urea can be produced, but the samples using the technique of hot pressing (120°C) to produce was impossible as they were all destroyed, the expansion of the press. It is assumed that this is a result of the downgrade, T_gand plastifitsirovanie urea. T_gsoy is much higher, so this problem did not arise in the case of resins on the basis of the soy/urea.

Use soy flour with low content of urease (a type of roasted soybeans) has allowed the development of a simplified single-stage approach. Fig and 18 show the effect of temperature and the number of stages (one or two) for a product based on soy/urea. The results suggest that roasted soybeans, all of the examples have shown themselves to be weak in adhesive strength as compared with not roasted soybeans with higher PDI (index of dispersion of protein), above.

As for the combinations based on the roasted soybeans, obtained at a lower temperature resin showed higher bond strength, it is very remarkable is the fact that they showed the significance of the considerable increase of the specified strength in the wet state (example 15). Surprisingly, the same high adhesive strength in the wet state showed a 3-layer samples using adhesives of fried flour made on the basis of low-temperature single-stage approach.

Estimation method (3-layer panel from maple wood): curly bars made from 3-ply maple panels were merged as at room temperature (45 min), and at 150°C (5 min). The results of their evaluation are graphically shown in Fig and 20 and described in table. As expected, because the samples were much larger samples produced for evaluation by the method of ABES, the decrease in T_gobserved when adding urea, intensified to the point where even contains 25% urea samples showed some delamination immediately after exiting the hot press. These modified urea samples did not have sufficient adhesive strength after the release of the hot press because of their low T_g. Generally speaking, this has not been a problem in the case of samples on the basis of the soy/urea, except for the samples with the level of PVA replacement of 50%, but in the present example, the level of soy/urea was very low - 0,54, resulting urea was just too high and the decrease in T_gprobably has again become a problem.

All samples cold extrusion is demonstrated excellent performance resins based on soy/urea/PVA with the level of PVA replacement of 25% (75% PVA), quite comparable in most of the samples. Was surprised by the fact that in this test the sample with the level of PVA replacement 50% showed degraded performance, which is probably due to the lower solids content in it. The proportion of unsatisfactory results in the testing of wood, glued together using all of these resins, ranged from 0% to 60%, although the entire set of received data failed to reveal any definite trend.

Examples 19-27

Adhesives based on soy/urea/PVA with the addition of a crosslinking agent. By adding adhesive on the soy/urea in PVA emulsion introduced the concept of functionality in the chemistry of the resins. This input functionality can be used to give a high resistance and PVA resins by the addition of a reactive cross-linking agent capable of reacting with soy, PVA or with soy, and PVA. Four different reactive cross-linking agent added to the adhesive system at levels of 2.5% and 10% soy/urea to assess their potential in making the adhesion strength in the wet state this stable compatible emulsions.

A method of manufacturing the resin-based soy/urea/PVA without doba is of a cross-linking agent was manufactured by a process described in example 11. Reactive cross-linking agents were added to the resin with rapid stirring. It was estimated following cross-linking agents: example 19 without using a crosslinking agent; example 20 to 2.5% PARADISE; example 21 - 10,0% PARADISE; example 22 to 2.5% pMDI; example 23 - 10,0% pMDI; example 24 - 2,5% AR550; example 25 - 10,0% AR550; example 26 - 2,5% Arlon; example 27 - 10,0% Arlon.

Discussion (evaluation method ABES/Instron): adding a reactive cross-linking agents increased adhesive strength when wet PVA-modified adhesives. For example, adding AR550 and Arlon showed no further increase the adhesion strength of the resin in the wet state (Fig).

Example 28

The dispersion of the soy/urea/PF: in addition to adding a co-adhesive on the soy/urea to PVA was also conducted comparative evaluation with phenol-formaldehyde (PF) dispersion.

Cooking method: PF-dispersion prigotovlyalos at room temperature in a round bottom flask of 250 ml, equipped with only an outboard mixer. PF-resin (laboratory) manufacturing, F/P=2,1; Na/P=0,2) were placed in a flask together with surface-active substance (all reagents were used at room temperature). After stirring for 2-3 minutes in a rapidly stirred solution of PF was introduced 2,2 g H₂SO_{4 . PF-resin inverted into low-viscosity dispersion in white. Then quickly stir the variance in the continuation of 5 min was injected resin-based soy/urea from example 11, the total mixture was vestibules for an additional 5 minutes, after which the pH was set by adding 0.9 g of 50% H2SO4. The dispersion of the soy/urea/PF was viesulas for 10 minutes to form a stable product with a low viscosity. Characteristics of the obtained resin and an analysis of its adhesive strength under shear are presented in tabl.}

Discussion (evaluation method ABES/Instron): bond strength of resin-based soy/urea increased significantly as a result of adding the dispersion PF-resin, which also served as a viable cross-linking agent. The resin had a light color, low viscosity, but lost its thixotropic nature, usually observed in soy resins. The results Fig clearly show excellent adhesive strength in the wet state, which bought the product with a high level of modification of soy, especially at high (150°C) temperature pressing. This example demonstrates the possibility and feasibility of combining soy/urea with PF-dispersion and achieve a high level of water resistance.

1. Method for the production of stable adhesive,including:
- denaturation of soy flour, providing, in essence, heat treated soy flour in an aqueous solution at a temperature of at least 40°C to 100°C, to obtain denatured soy flour, essentially free of urease, and
- adding urea to the denatured soy flour, receiving adhesive based on soy flour.

2. The method according to claim 1, in which the denaturation of soy flour carried out by heating to a temperature of at least 81-100°C.

3. The method according to claim 1, in which the denaturation of soy flour can be performed during a time period from 15 to 500 minutes

4. The method according to claim 1, wherein the soy flour contains at least 20 wt.% carbohydrates.

5. The method according to claim 1, wherein the urea is added to the denatured soy flour in an amount equivalent to a maximum of five parts of urea per part of soy flour.

6. The method according to claim 1, comprising adding a cross-linking agent in the adhesive based on soy flour.

7. The method according to claim 6, in which a crosslinking agent is not containing formaldehyde cross-linking agent selected from isocyanate, polyaminoamidazolines resins, epoxy resins, aldehyde resins, aldehyde starch, mcevisualaid resin and mixtures thereof.

8. The method according to claim 6, in which the crosslinking agent is a polymeric methylene-diphenyl-diisocyanate.

9. The method according to claim 6, in which a crosslinking agent selected the play of politicalintelligence resin, polyalkyleneglycol or aminopropionitrile resin.

10. The method according to claim 6, in which the crosslinking agent is dialdehyde starch.

11. The method according to claim 6, in which the crosslinking agent is glyoxal.

12. The method according to claim 6, in which the crosslinking agent is moevenpick.com.

13. The method according to claim 6, in which a crosslinking agent is added in an amount of from 0.1 to 80 wt.%.

14. The method according to claim 1, also comprising drying the adhesive on the basis of soy flour to obtain a powdery adhesive.

15. The method according to claim 6, in which the crosslinking agent is formaldehydefree cross-linking agent selected from formaldehyde, phenolformaldehyde, modelinformation, melamineformaldehyde, phenolresorcin and any combination thereof.

16. The method according to claim 6, in which the crosslinking agent is phenolformaldehyde.

17. The method according to claim 6, in which the crosslinking agent is modelinformation.

18. The method according to claim 1, comprising adding a diluent to the adhesive on the basis of the soy flour.

19. The method according to p, in which the diluent is selected from glycerol, ethylene glycol, propylene glycol, neopentyl glycol and polymeric species.

20. The method according to p, in which the solvent is glycerin.

21. Method for the production of a stable dispersion adhesive based on denatured soy is uki and urea, including:
- heat treatment of soy flour to obtain denatured soy flour, essentially free of urease, while denaturation of soy flour carried out by heating it to a temperature at least 81°C to 100°C,
- adding urea to the denatured soy flour, receiving adhesive based on soy flour, and
- addition polymer, which is selected from polyvinyl acetate or phenol-formaldehyde dispersions in adhesive based on soy flour, with the formation of a stable dispersion adhesive based on denatured soybean flour and urea.

22. The method according to item 21, in which the polymer is emulsified or dispersed polymer.

23. The method according to item 21, in which the denaturation of soy flour can be performed during a time period from 15 to 500 minutes

24. The method according to item 21, in which the urea is added to the denatured soy flour at a temperature of soy flour 81-100°C.

25. The method according to item 21, in which soy flour contains at least 20 wt.% carbohydrates.

26. The method according to item 21, in which the urea is added to the denatured soy flour in an amount equivalent to a maximum of five parts of urea per part of soy flour.

27. The method according to item 21, comprising adding a crosslinking agent to the dispersion of soy flour/urea.

28. The method according to item 27, in which a crosslinking agent is not containing four the aldehyde cross-linking agent, choose from a polymeric methylene-diphenyl-diisocyanate, polyaminoamidazolines resin, epoxy resin and glyoxal.

29. The method according to item 27, in which a crosslinking agent is added in an amount of from 0.1 to 80 wt.%.

30. The method according to item 27, in which the crosslinking agent is formaldehydefree cross-linking agent selected from formaldehyde, phenolformaldehyde, modelinformation, melamineformaldehyde, phenolresorcin and any combination thereof.

31. The method according to item 21, also comprising drying the dispersion of soy flour/urea to obtain a powdery dispersion of soy flour/urea.

32. The method according to p, in which the drying of a dispersion of soy flour/urea carried out by freeze-drying method.

33. The method according to p, in which the drying of a dispersion of soy flour/urea realized by means of spray drying.