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    • 专利摘要:
    soybean urea adhesives denatured with stable acid and methods for their manufacture. the present invention relates to an improved method of producing a stable acid-denatured soy / urea adhesive having improved wet and dry strength, with more efficient production and lower production costs. The method comprises combining urea with soy flour which has been treated with acid until denatured and substantially free from urea activity. the soy flour is preferably reduced to a pH of 2.0 to 4.0 for at least 1 minute. optionally, the method may also include adding a crosslinking agent, diluent or both to the soy flour / urea adhesive and / or adding an emulsified or dispersed polymer. adhesives and dispersions prepared according to the methods of this invention offer greater stability and strength properties.
    公开号:BR112012004391B1
    申请号:R112012004391-9
    申请日:2010-08-27
    公开日:2020-10-13
    发明作者:Michael J. Birkeland；James M. Wescott
    申请人:Solenis Technologies Cayman, L.P；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [0001] The present invention relates to a composition and method of manufacturing a stable adhesive by combining urea and soy flour that has been denatured with acid and substantially free of urea to form a soy / urea adhesive. stable. BACKGROUND OF THE INVENTION
    [0002] Soy flour-derived adhesives containing protein first came into general use during the 1920s (see, for example, U.S. Patents 1,813,387, 1,724,695 and 1,994,050). The soy flour suitable for use in adhesives has been, and still is, obtained by removing some or most of the soy oil, which produces a residual soy flour that has subsequently been ground into extremely fine soy flour. Typically, hexane is used to extract most non-polar oils from crushed soybeans, although extrusion / extraction methods are also suitable means for removing oil.
    [0003] The resulting soy flour was then generally denatured (ie, the secondary, tertiary and / or quaternary structures of the proteins were altered to expose the additional polar functional groups capable of binding) with an alkaline agent and , to some extent, hydrolyzed (ie, covalent bonds have been broken) to produce adhesives for gluing wood under dry conditions. However, these early soy adhesives showed poor water resistance, strictly limiting their use for domestic applications.
    [0004] In addition, common soy adhesives in the prior art have a limited useful life. After just a few hours, the viscosity and performance of the alkaline-denatured soy flour mix decreases rapidly. This reduction in performance is believed to be a result of some hydrolysis of soy flour and the excessive decomposition of secondary, tertiary and quaternary structures considered to be important for the formation of strong adhesive and cohesive bonds. Thus, there is a need for an adhesive that demonstrates a balance between the exposure of sufficient functional groups to improve performance, while retaining sufficient protein structure to maintain adhesive performance and provide stability.
    [0005] In the 1920s, phenol-formaldehyde (PF) and urea-formaldehyde (UF) adhesive resins were initially developed. The phenol-formaldehyde and modified urea-formaldehyde resins were externally durable, but had high raw material costs that initially limited their use. World War II contributed to the rapid development of these adhesives for applications resistant to water and weather conditions, including external applications. However, protein-based adhesives, mainly soy-based adhesives that have often been combined with blood or other proteins, have continued to be used in many indoor applications.
    [0006] Currently, interior plywood, medium density fiberboard (MDF) and agglomerates (PB) are mainly produced using urea-formaldehyde resins. Although very strong, fast curing, and reasonably easy to use, these resins lack hydrolytic stability along the main polymer chain. This causes significant amounts of free formaldehyde to be released from finished products (and ultimately, inhaled by occupants inside the home). There have been several legislative actions to pressure the reduction of formaldehyde emissions when used in indoor domestic applications (Health and Safety Code Title 17 California Code of Regulations Sec, 93120-93120.12, and the new United States national standard- Reference: 2010 U.S. S1660).
    [0007] Soy-based adhesives can use soy flour, soy protein concentrates (SPC), or soy protein isolates (SPI) as the starting material. For simplicity, the present disclosure refers to all soy products that contain more than 20% carbohydrates such as "soy flour". Soy flour is less expensive than SPI, but soy flour contains significant levels of activated urea (an enzyme that breaks down urea quickly and efficiently into ammonia), thus requiring a need for urea to be deactivated when urea is used in final adhesive. This needs to be done without compromising the viscosity / solids ratio or the performance of the final product. Soy flour also contains high levels of carbohydrates, which requires a more complex cross-linking technique, since cross-linking results in the much improved water resistance of soy-based adhesives.
    [0008] SPC contains a greater amount of protein than soy flour, but contains less protein than SPI. Typically, SPC is produced using an alcohol wash to remove soluble carbohydrates.
    [0009] SPI is typically produced through an isoelectric precipitation process. This process not only removes soluble sugars, but also removes the most soluble low molecular weight proteins, leaving behind mainly high molecular weight proteins that are ideal for adherence even without modification. As a result, SPI produces a very strong adhesive with appreciable durability. However, SPI is very expensive, and therefore is not an ideal source of soy for soy-based adhesives. Thus, there is a strong need to produce high quality adhesives from soy flour.
    [0010] U.S. Patent 7,252,735 to Li et al. (Li) describes soy protein cross-linked with a resin derived from polyamido-amine epichlorohydrin (PAE). Li describes these particular PAEs, which are known wet strength additives for role, in many possible reactions with functional protein groups. In Li, SPI is denatured with alkali at hot temperatures and then combined with a suitable PAE resin to produce a water resistant bond. This aqueous soy solution must be prepared immediately before copolymerization (or lyophilized) to take into account an appropriate service life. Li does not teach or suggest the importance of soy denaturation for use with PAE, since the SPI used in Li already has a long thermal history. In addition, the alkaline process described by Li is not sufficient to deactivate urea in soy flour and is therefore an inappropriate approach for producing soy flour / urea adhesives. In addition, the adhesives described by Li suffer from at least one of the following: high viscosity, low solids, or poor stability.
    [0011] US Patent π ° 6,497,760 to Sun et al. (Sun) also teaches soy-based adhesives produced from SPI as a starting material. Sun teaches that SPI can be modified with urea, but Sun does not teach or suggest modifying soy flour with urea to provide an improved soy flour based adhesive. Urea is a known denaturant for adhesives that do not have significant urea activity, such as SPI. However, urea is problematic for soy flour as it contains moderate to high levels of urea activity. Although it is known that SPI can be denatured with urea (see, for example, Kinsella, J. Am. Oil Chem. Soc, March 1979, 56: 244), Sun teaches at a distance the use of urea with soy flour due to urea activity associated with it.
    [0012] There is very limited previous work that describes some methods for deactivating urea in soy flour and there is no work that describes this particular form of treatment with acid.
    [0013] US Patent No. 3,220,851 to Rambaud describes a method of treating soybeans to improve their quality and usability in food processing. Rambaud describes cooking soy in an aqueous solution at temperatures that do not exceed 80 ° C, in order to remove "undesirable" compounds such as urea and anti-trypsin from soy. Rambaud specifically teaches that the temperature of 80 ° C constitutes a limit value beyond which the rate of degradation of albumin increases rapidly, and it is therefore essential not to exceed this value. Nor does Rambaud teach or suggest why removing urea or antitrypsin may be useful for soybeans with respect to their ability to serve as adhesives.
    [0014] Wescott (U.S. Ped. # 11 / 779,558) also teaches a higher temperature method for treating soy to disable urea. This method, while effective in deactivating urea, is inferior to this invention in that it results in a significant increase in viscosity and color compared to this invention.
    [0015] U.S. Patent No. 7,345,136 to Wescott describes a method for denaturing soy flour in preparation for copolymerization by the direct addition of formaldehyde. Such a method if applied to this invention would result in high levels of ammonia and significant decreases in performance. Alternatively, if the method of this invention is applied to the Wescott process (7,345,136), immediate gelation is performed when formaldehyde is added to denatured soy flour. This is a result of an insufficient level of denaturation for the process. SUMMARY OF THE INVENTION
    [0016] The present invention provides a method of making stable adhesives by combining soy flour that has been denatured with acid and substantially free of urea and urea activity to form a stable soy / urea adhesive. The present invention also provides a stable composition comprising soy flour which is denatured with acid and substantially free from urea and urea.
    [0017] In one embodiment of the present invention, soy flour is dispersed in water and the pH is reduced through the isoelectric point to a pH of less than 4.5, preferably less than 4.0, but greater than than 2.0 and allowed to stir for at least 1 minute. This acid-denatured soybean is then substantially free of urea as determined by pH stability after the addition of urea (i.e., no ammonia formation). Urea can then be added to the material at any pH after this stage of acid denaturation.
    [0018] The pH of the final adhesive composition, with or without added crosslinker can vary from 2 to 10. Preferably, from 3.5 to 8.0. Typically, the pH is adjusted to control the rate of reaction or stability of the final adhesive. Any suitable acid or base can be used to change the pH.
    [0019] Denaturation with acid is typically conducted at room temperature, but it is reasonable to conduct the denaturation step at any temperature between 5 to 50 ° C.
    [0020] The soy / urea adhesive may further include a cross-linking agent, an emulsified polymer, a diluent, or any combination thereof.
    [0021] In the present invention, the addition of urea to the soy flour that has been denatured with acid and substantially free from urea produces a soy / urea adhesive with one or more of the following properties: excellent stability, compatibility, dry resistance or wet and biological resistance. In addition, the present invention results in much lighter colored adhesives and significantly higher solids contents (25% higher) than previously reported.
    [0022] Furthermore, the present invention advantageously uses Baker quality soy flour with a high content of regular PDI, available at a much lower cost than conventional soy protein sources for adhesives. Typically, regular Baker quality soy flour does not offer any appreciable adhesive capacity unless a denaturing step and / or crosslinking agent is used. Advantageously, the present invention demonstrates that urea can be used very effectively to provide additional denaturation and solvation for acid-denatured soy flour. The present invention provides a stable acid-denatured soy / urea adhesive that has improved properties even without a cross-linking agent.
    [0023] In fact, the stable adhesives based on acid-denatured soy flour of the present invention offer excellent resistance to biological attack for at least several months.
    [0024] The new methods of the present invention provide stable soy / urea adhesives and adhesive dispersions having several advantages over the prior art. First, the adhesives / dispersions of the present invention have much lower viscosities compared to other soy-based adhesives containing urea in the same solids content, which takes into account easy transfer and applications. Second, the adhesives of the present invention are much lighter in color. Third, the adhesives of the present invention have a much higher percentage of soy solids content; up to 25% higher solids compared to heat treated denatured products having the same viscosity. Fourth, the adhesives of the present invention demonstrate superior shelf life with certain crosslinking agents. BRIEF DESCRIPTION OF THE FIGURES
    [0025] Figure 1: 12HU (Example 2) vs. 12AUB (Example 4) @ 54% solids - viscosity and viscosity stability at room temperature.
    [0026] Figure 2: 12HU (Example 2) vs. 12AUB (Example 4) @ 54% solids - pH and pH stability at room temperature.
    [0027] Figure 3: pH and viscosity stability of Example 7 (11ABU-50).
    [0028] Figure 4: Viscosity stability of Examples 10 (50-pMDI) and 11 (100-pMDI) at room temperature.
    [0029] Figure 5: curing rate curves of Examples 12, 14 and 16. DETAILED DESCRIPTION OF THE INVENTION
    [0030] In the specification and in the claims, the terms "including" and "comprising" are unlimited terms and should be interpreted as "including, but not limited to ....". These terms encompass the most restrictive terms "consisting essentially of" and "consisting of".
    [0031] As used herein and in the appended claims, the singular forms "one", "one", "o" and "a" include the plural reference unless the context clearly dictates otherwise. Likewise, the terms "one" (or "one"), "one or more" and "at least one" can be used interchangeably here. It should also be noted that the terms "comprising", "including", "characterized by" and "having" can be used interchangeably.
    [0032] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as normally understood by a person of ordinary skill in the technique to which this invention belongs. All publications and patents specifically mentioned herein are incorporated by reference in their entirety for all purposes, including the description and disclosure of the chemicals, instruments, statistical analyzes and methodologies that are reported in the publications that can be used in connection with the invention. All references cited in this specification are to be taken as indicative of the skill level in the technique. Nothing here should be construed as an admission that the invention has no right to predate such disclosure by virtue of the previous invention.
    [0033] The present invention provides a new adhesive and adhesive dispersion produced by combining urea with soy flour, where the soy flour has been denatured with acid and substantially free from urea activity. Urea can be added to acid-denatured soy flour without degradation of urea urea, and thus a stable product can be produced.
    [0034] By "stable" is meant an adhesive that remains viscous and stable at pH for long periods at room temperature. By "pH stable" is meant that the pH is within one unit for at least twenty days. By "viscous stable" is meant that the Brookfield viscosity of the adhesive will remain within 25% of its initial viscosity for 5 hours or, as measured after 24 hours, it will remain within 35% of its initial viscosity for at least 7 days.
    [0035] By "denatured" is meant proteins that have lost part of their structure (quaternary, tertiary and secondary structure) through the application of a little external tension or compound, such as, for example, the treatment of proteins with acids or strong bases, high concentrations of inorganic salts, organic solvents (eg, alcohol or chloroform), or heat. Soy flour, when properly denatured, is an excellent adhesive. Once denatured, the proteins contained within the "unrolled" soy flour from its native structure, thus exposing the most hydrophilic groups in the main chain of the protein.
    [0036] By "substantially free" is meant that conventional tests will not recognize any significant amounts of urea present in heated soy flour, typically measured by a change in pH over time. Thus, soy flours that are "substantially free" of urea activity will experience a pH change of less than one unit for twenty days in the presence of urea at room temperature.
    [0037] Although a soy flour that is substantially free of urea is denatured, a soy flour that has been denatured does not need to be substantially urea free. The novelty of the present invention is that the inventors have determined that a slight stage of acid denaturation is sufficient to denature a soy flour in such a way as to make the soy flour substantially free from urea, and therefore useful for the adhesive. stable soybean / urea. Interestingly, a light or even extreme denaturation process is not effective in deactivating urea.
    [0038] By "denatured acid" is meant to reduce the pH of soy flour to less than 4.5, preferably to 4.0, but not lower than 2.0, for a period of at least 1 minute.
    [0039] One aspect of the present invention provides a method for producing a stable adhesive, the method comprising the steps of providing an aqueous suspension of soy flour, reducing the pH of the soy flour to less than 4.5, preferably 4.0 or less until denatured and substantially free from urea; and adding urea to the soy flour, in which a stable aqueous soy / urea adhesive is formed. In general, soy flour is denatured in less than 30 minutes, preferably less than 15 minutes. Soy flour can be treated with acid for more than 30 minutes.
    [0040] The present invention produces stable aqueous soy / urea adhesives independently of the PDI of the soy flour used. The Protein Dispersibility Index (PDI) is a means of comparing the solubility of a protein in water, and is widely used in the soy product industry. A sample of the soybeans is ground, mixed with a specific amount of water, and then mixed together at a specific rotation for a specific time. The protein content of the resulting mixture and the original bean flour is then measured using a combustion test, and the PDI is calculated as the percentage of the protein in the mixture divided by the percentage in the flour. For example, a PDI of 100 indicates total solubility. PDI is affected not only by the type of soybeans used, but also by any manufacturing processes used in the soybeans. For example, heat can decrease the PDI of a soy sample. The required PDI of a soy flour is dependent on the purpose for which the soy beans are to be formulated. The utility of the present invention is that the soy / urea adhesive of the present invention can use high or low PDI soy flour to produce the stable adhesives of the present invention. The acid denaturation stage is so effective that even flours with high levels of urea (high PDI) are equally effective and may still be preferred in some cases.
    [0041] It is absolutely essential to reduce the pH of the soy flour of the present invention until denatured with acid and substantially free from urea. The acid used to treat soy flour can be a Bronsted or Lewis acid classification. The use of common mineral acids, such as sulfuric, nitric, phosphoric or hydrochloric acid is preferable.
    [0042] Soy flour denatured with conventional heat has very high viscosities and low levels of solid, making it difficult to transport and store. Acid denatured soy / urea adhesives are substantially higher in solids and lower in viscosity than heat-treated adhesives of similar composition. The solids content of denatured soy / urea adhesives in some cases can be more than 25% higher than heat denatured products with similar compositions while maintaining a similar viscosity.
    [0043] The amount of urea added to the soy flour depends on the needs of the soy / urea adhesive or dispersion. For example, the urea content can be adjusted to control the flow characteristics or the glass transition temperature (Tg) of the final adhesive. This allows the adhesive / dispersion of the present invention to be spray dried and converted to a usable powder adhesive resin.
    [0044] In one embodiment, the amount of urea added to the soy flour can be from about five parts of urea for one part of soy flour (solids / solids) to about 0.1 part of urea for one part of soy flour (solids / solids); more preferably between two parts of urea for a part of soy flour to about 0.5 part of urea for a part of soy flour. Soy flour can be denatured with acid before, during or after the addition of urea. Preferably, the soy flour is denatured with acid before the addition of urea, but with low PDI flours, it is possible to reverse the order of addition.
    [0045] The adhesive of the present invention can be added to any emulsion polymer, such as, for example, polyvinyl acetate (PVAc) emulsions, to produce a stable adhesive dispersion. The emulsion polymer is added at a level of 0.1 to 80% by weight of dry solids based on the dry solids weight of the total adhesive (total adhesive is the adhesive formulation, including, but not limited to, soy , urea, any crosslinker added, and any diluent added). By "emulsion" is meant a suspension of small globules of a liquid in a second liquid where the first liquid will not mix (that is, oil in vinegar). By "dispersion" is meant a two-phase adhesive system in which one phase is suspended in a liquid. In consideration of convenience, the emulsion or dispersion of the present invention is referred to throughout this document as an "adhesive dispersion" or "dispersion". This does not mean limiting the scope of the invention, but it is only for ease of reading.
    [0046] Typically, the addition of unmodified soy flour or soy flour denatured with NaOH directly to the emulsified polymer produces resins having poor stability and compatibility. In contrast, the addition of the stable acid-denatured soy / urea adhesive of the present invention to an emulsion or dispersed polymer produces a highly compatible stable adhesive dispersion useful in many industrial applications. In addition, the combination is performed by simple mixing techniques using commercial mixing tanks, dilution tanks or reactors known to a person skilled in the art. The temperature of the mixture is not considered to be critical and room temperature is typically employed, although it may be desirable and acceptable to combine the stable soy / urea adhesive of the present invention with the emulsion or polymer dispersed at higher temperatures depending on the needs of the user. Adjustment of the final pH with acids or bases may be necessary to ensure optimal dispersion stability. However, these adjustments are typically quite modest and are known to a person of skill in the art. For example, minor adjustments necessary for the stability of the emulsion or dispersion may be desired.
    [0047] The stable acid-denatured soy / urea adhesive of the present invention can be used as is or can be further improved by the addition of a suitable crosslinking agent. Crosslinking agents are typically added to resins and adhesives to provide additional properties or to manipulate existing adhesive properties, such as water resistance, solubility, viscosity, shelf life, elastomeric properties, biological resistance, strength, and more. The role of the crosslinking agent, regardless of type, is to incorporate an increase in crosslinking density within the adhesive itself. This is best achieved with crosslinking agents that have several reactive sites per molecule.
    [0048] The type and amount of crosslinking agent used in the stable acid-denatured soybean / urea adhesive of the present invention depends on which properties are desired. In addition, the type and amount of crosslinking agent used may depend on the characteristics of the soy flour used in the adhesive.
    Any cross-linking agent known in the art can be used in the method of the present invention. For example, the crosslinking agent may or may not contain formaldehyde. Although formaldehyde-free cross-linking agents are highly desirable in many indoor applications, formaldehyde-containing cross-linking agents remain acceptable for some external applications.
    [0050] Possible formaldehyde-free crosslinking agents for use with the adhesives of the present invention include isocyanates such as polymeric methyl diphenyl diisocyanate (pMDI) and polymeric hexamethylene diisocyanate (pHMDI), amine-epichlorohydrin adducts, epoxy, aldehyde and urea-aldehyde resins capable of reacting with soy flour. When a formaldehyde-free crosslinking agent is employed in the present invention, it is used in amounts ranging from 0.1 to 80% on the dry weight basis of the total dry adhesive (total adhesive is the adhesive formulation, including, but not limited to thereto, soy, urea, any crosslinker added, and any diluent added). A preferred formaldehyde-free cross-linking agent comprises a polyamidoamine epichlorohydrin (PAE) and is used in amounts ranging from 0.1 to 80% dry weight.
    [0051] Amino-epichlorohydrin resins are defined as those prepared by reacting epichlorohydrin with functional amine compounds. These include polyamidoamine-epichlorohydrin resins (PAE resins) and polyalkylene polyamine-epichlorohydrin (PAPAE resins) and amine-epichlorohydrin polymer resins (APE resins). PAE resins include functional amine based azetidinium PAE resins such as Kymene ™ 557H, Kymene ™ 557LX, Kymene ™ 617, Kymene ™ 624 and Hercules CA1000, all available from Hercules Incorporated, Wilmington DE, functional epoxy based resins in tertiary polyamide amine and functional epoxy PAE resins based on tertiary polyamidourylene amine such as Kymene ™ 450, available from Hercules Incorporated, Wilmington DE. A suitable crosslinking PAPAE resin is Kymene ™ 736, available from Hercules Incorporated, Wilmington DE. Kymene ™ 2064 is an APE resin that is also available from Hercules Incorporated, Wilmington DE. These are widely used commercial materials. Its chemistry is described in the following reference: H. H. 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). It is also possible to use low molecular weight amine-epichlorohydrin condensates as described in Coscia (US Patent No. 3,494,775) as formaldehyde-free crosslinkers
    [0052] Possible formaldehyde-containing crosslinking agents include formaldehyde, phenol formaldehyde, urea formaldehyde, melamine urea formaldehyde, melamine formaldehyde, phenol resorcinol and any combination of these. When formaldehyde-containing crosslinking agents are employed in the invention they are used in amounts ranging from 1 to 80% of the total adhesive composition based on dry weight (total adhesive is the adhesive formulation, including, but not limited to, soy, urea, any crosslinker added, and any diluent added). In one embodiment of the invention, the crosslinking agent comprises phenol formaldehyde in amounts ranging from 1 to 80%, by dry weight.
    [0053] Regardless of the specific crosslinking agent used, the crosslinking agent is typically added to the acid-denatured soy / urea adhesive immediately before use (as such in the production of a lignocellulosic composite), but can be added in days or even weeks before use in some situations.
    [0054] In some applications, it may be desirable to add a diluent to improve the solvate, still denature or otherwise modify the physical properties of the acid / denatured soy / urea dispersion. Possible diluents / modifiers include polyols such as glycerol, ethylene glycol, propylene glycol, neopentyl glycol, the polymer version of these, or any other monomer containing hydroxyl or other available polymeric material, defoamers, wetting agents and more than are commonly used in the art. Other diluents that only serve to prolong solids are also acceptable, such as flour, talc, clays and more.
    [0055] These diluents / modifiers can be incorporated in levels ranging from 0.1 to over 70% by weight of the total adhesive based on the dry weight of solids. These can be incorporated during any stage of the process including before, during or after the urea deactivation heating step.
    [0056] The use of traditional soy protein modifiers can also be used; such as the addition of sodium bisulfite to reduce viscosity by reducing disulfide bonds.
    [0057] The final pH of the acid-denatured soy / urea adhesives of the present invention can be adjusted with any suitable Bronsted or Lewis acid or base. The final pH of the acid-denatured soy / urea adhesive is less than 10, preferably less than 7 and greater than 2.0, preferably greater than 3.0. In one version, adhesives having a pH between three and seven have ideal stability and compatibility. A person skilled in the art will understand how to manipulate the pH of the adhesive (described in the examples below) and what applications require an adhesive having a higher or lower pH. A unique aspect of the present invention is the wide range of usable pH values. Typically, the final pH will be selected based on the application or the type of crosslinker used. For example, with PF and PAE resins, higher pH soy / urea adhesives will be preferred and for pMDI and UF or MUF resins, lower pH soy / urea adhesives will be preferred. Although for PF dispersions, a low pH may be preferable.
    [0058] The method of the present invention can also include the addition of a spray or lyophilization step to produce a powder adhesive.
    [0059] The stable soy / urea adhesive of the present invention can be used in many industrial applications. For example, the adhesive can be applied to a suitable substrate in amounts ranging from 1 to 25% dry weight (1 part dry adhesive per 100 parts substrate to 25 parts dry adhesive per 100 parts substrate), preferably in the range of 1 to 10% by weight and more preferably in the range of 2 to 8% by weight. Examples of some suitable substrates include, but are not limited to, a lignocellulosic material, pulp or fiberglass. The adhesive can be applied to the substrates by any means known in the art including roller coating, blade coating, extrusion, curtain coating, foam coaters and spray coaters such as a spinning disc resin applicator.
    [0060] A person of skill will understand how to use adhesives / dispersions of the present invention to prepare lignocellulosic composites using the references known in the field. See, for example, "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, Wl (1999). Various materials can be prepared using the adhesive / dispersion of the invention including agglomerates, oriented particle boards (OSB), wafer board, fiber board (including medium density and high density fiber board), cut wood strand parallel (PSL), cut wood strand laminated (LSL), cut wood strand oriented (OSL) and other similar products. Lignocellulosic materials such as wood, wood pulp, straw (including rice, wheat or barley), flax, hemp and bagasse can be used in the manufacture of the thermo-curing products of the invention. The lignocellulosic product is typically produced by mixing the adhesive with a substrate in the form of powders, particles, fibers, chips, flake fibers, platelets, finials, shavings, sawdust, straw, stalks or canes and then compression and heating of the resulting combination to get the material cured. The moisture content of the lignocellulosic material must be in the range of 2 to 20% before mixing with the adhesive of the present invention.
    [0061] The adhesive of the present invention can also be used to produce plywood or laminates (LVL). For example, in one embodiment, the adhesive can be applied to surfaces veneered by roller coating, blade coating, curtain coating, or spraying. A plurality of veneers are then stored to form sheets of the required thickness. The mats or sheets are then placed on a press (for example, a printing roll), usually heated, and compressed to effect the consolidation and curing of the materials on a plate. The fiber board can be produced by the wet felt / wet compression method, the dry felt / dry compression method, or the wet felt / dry compression method.
    [0062] In addition to lignocellulosic substrates, the adhesives of the present invention can be used with substrates such as plastics, glass wool, fiberglass, other inorganic materials and their combinations.
    [0063] The following examples are, of course, offered for illustrative purposes only, and are not intended to limit the scope of the present invention in any way. In fact, various modifications of the invention in addition to those shown and described in this document will become evident to those skilled in the art from the previous description and the following examples and fall within the scope of the appended claims.
    [0064] Examples and Evaluation Methodologies.
    [0065] The following characteristics of the acid-denatured soy / urea adhesives were evaluated: 1) Physical Properties - Brookfield viscosity (RV @ 10 RPMs in all cases) with spindle selection depending on product viscosity, pH and stability at room temperature (viscosity and biological - as determined by the obvious onset of soy that rot or spoil similar to milk). To reduce the impact of a temporary increase in viscosity, often due to the thixotropic nature of soy adhesives, the adhesive is quickly agitated for 30 seconds before any viscosity measurement. 2) Development of dry strength - shear force of two pressed filaments using the Automated Bonding Evaluation System (ABES) from AES, Inc. This is used to determine the strength of the adhesive bond as developed over time under time / specific pressure temperatures. In all examples 120 ° C was used. The results are plotted in relation to the compression time to determine the development of the relative strength of different adhesives as a function of time. Specimens are prepared and tested according to the ABES Procedure. 3) Adhesive Bond Strength - As determined by the following ABES procedure: ABES Procedure.
    [0066] Sample preparation: The wood samples were stamped using the Automated Bonding Evaluation System (ABES) stamping mechanism of tai veneers so that the final dimensions were 11.7 cm across the grain, 2.0 cm perpendicular to the grain and 0.08 cm thick. The adhesive to be tested was applied to one end of the sample in such a way that the entire overlapping area is covered, generally being in the range of 3.8 to 4.2 mg / cm2 on a wet basis. The sample was then attached to a sheet of plywood (open time of less than 15 seconds to ensure excellent transfer) and placed in the ABES unit in such a way that the overlapping area of the attached samples was 1.0 cm per 2.0 cm. Unless otherwise mentioned, all samples were pressed for 2.0 minutes at 120 ° C, with 9.1 kg / cm2 of pressure. All bound samples were then allowed to condition for at least 48 hours in a controlled environment at 22 ° C and 50% relative humidity.
    [0067] Resistance Test: For each resin, ten samples were prepared as described above. After conditioning, five of the ten samples were tested using the ABES instrument in the dry condition. The maximum load after breaking the sample was recorded. These were called dry resistance samples. The remaining five samples were placed in a 22 ° C water bath for four hours. The samples were removed from the water bath and tested immediately in the manner described above. These samples were called wet samples. For each resin, the reported value is an average of the five samples. The reported error is the standard deviation. Typical coefficients of variation (VOCs) for this method are around 15% for both dry and wet assessments; this is considered to be excellent considering the variability within the wood itself.
    [0068] 4) Agglomerate Procedure: The purpose of this procedure is to outline the approved process for preparing agglomerates using a 1.22 m (48 ") diameter rotary mixer with a 1.27 mx 1 air atomizer, 27 m (50 "x 50") of pressure heated with steam. The target density and thickness for these panels was 46 PCF with a thickness of 0.02 m (% "). The face in relation to the nucleus was 40/60. The supply was the mixture of several western species (Roseburg Forest Products, 1.5 to 4.0% MC). The following procedure was followed to prepare agglomerates: Weigh the face supply in an approved container and load into the 1.22 m (48 ”) diameter mixer drum. Weigh the resin in such a way that 7.0% solid resin is used to dry the supply (nearest 0.0 g) and pour into the funnel connected to the mixer spray set. Turn on the air atomizer and adjust to 276 kPa (40 psi). Spray until all resin / additive has left the funnel and hose. Allow the mixer to revolve for at least 5 minutes to distribute the remaining atomized resin. Remove the supply from the mixer and place it in a well-labeled container. Take the moisture content of the matrix from this resin supply. Repeat for the core layer and the calculated load of 7.0% dry resin to dry the wood base. Place the release paper on a laboratory hood plate and a 0.5 m x 0.5 m (22 ”x 22”) formation box on top of the release paper. Weigh the supply for the first layer face to face to the nearest 0 g. Form the face layer by manually expanding the supply along the hood using a wide tooth comb to distribute the supply evenly. It is important that the layer is as evenly dispersed as possible to avoid density distribution problems. Weigh the core supply to the nearest 0 g (middle layer). Form the core layer by manually dispersing the supply across the top of the face layer with a wide tooth comb to distribute the supply evenly. It is important that the layer is as evenly dispersed as possible to avoid density distribution problems. Weigh the supply for the last face layer to the nearest 0 g. Form the face layer by manually dispersing the supply across the top of the core layer using a wide tooth-width comb to distribute the supply evenly. It is important that the layer is as evenly dispersed as possible to avoid density distribution problems. Place the cover inside the formation box on the top of the matrix formed by 3 layers and manually press firmly for 15 seconds. While keeping the cover under control, carefully lift the formation box out to expose the matrix. Then carefully check the coverage. Place the second piece of release paper (shiny side down) and the hood plate on top of the formed matrix. Place the formed matrix on the press loading area and slide it on the press using a thrust rod. Check that the temperature of the press rollers is 170 ° C. Press the CLOSE and CONFIRM CLOSURE buttons simultaneously on the PressMAN ™ system (as provided by the Alberta Research Council). The press must begin its cycle. Keep in such a thickness that the core is above 100 ° C for 60 seconds as measured using the PressMAN ™ temperature / pressure probe. As soon as the temperature time has been reached, move the cycle to the degassing phase and the press with open once the total cycle is complete. Remove the plate immediately using a push stick. Place the panels in an insulated box (hot box) for 24 hours. Remove the plates from the hot box and trim in 0.5 m x 0.5 m (20 ”x 20”). Calculate the density of each plate by measuring the thickness of the plate in each corner of approximately 0.05 m (2 ”) from the edges and at a point in the middle. Obtain an average thickness using these values and calculate the volume of the plate. Weigh the plate to obtain the mass and calculate the density as mass / volume in units of kg / m3 (lb / ft3). Label and cut the sample plates in such a way that each panel produces five samples of MOR / MOE and eight samples of internal bonding (IB). The condition of all test samples for at least 48 hours in a controlled environment at 26.6 ° C (80 ° F) and 30% relative humidity before testing.
    [0069] The raw materials for these examples are as follows: Soy Flour: Soy Flour-90 supplied by Cargill (Minneapolis, MN) 90 PDI, 200 mesh; Soy Flour-TS supplied by ADM (Decator, IL) 20 PDI, 100 mesh, Urea (Commercial Grade) acquired from Univar; PAE, Hercules CA 1300, supplied by Hercules, pH 3.5, solids = 30%; pMDI was Rubunate ™ FC3345, Huntsman International, Woodlands, TX; Advantage ™ 357 defoamer agent, supplied by Hercules Incorporated. PVAc: Duracet provided Franklin.
    [0070] The Examples are listed in tables and figures according to the following nomenclature: level of soy: urea (12 = 1 part of soy to 2 parts of urea), order of use of the process step: H = heat, A = addition of acid, B = addition of base, U = addition of urea, finally the% of theoretical solids is provided. For example, 12AUB-54 represents a product that has one part of soy to 2 parts of urea and was produced by the addition of acid, followed by urea, then base and was produced with 54% of theoretical solids.
    [0071] Example 1. Comparative Example # 1: Unsaturated Soy / Urea Adhesive (11U-26)
    [0072] Soy flour when combined with water contains a significant amount of active urea which reacts quickly with urea to produce ammonia. Ammonia is observed by rapidly increasing the pH to a pH around 9 and then by the evolution of ammonia gas in the system. In one example, a 15% solution of soy flour-90 was prepared at room temperature with a pH of 6.2. Urea was added in an amount of approximately 1 part of urea to 1 part of soy flour and the pH rose to 8.90 in less than 10 minutes. After 20 minutes the pH was 9.2 with a very strong ammonia odor. This sample is not stable and is not considered acceptable.
    [0073] Example 2. Comparative Example # 2: Heat-denatured soy / urea adhesive (12HU-54)
    [0074] The soy flour was denatured with heat and then combined with urea to produce stable aqueous soy / urea products by the method described by Wescott (U.S. Ped. No. 11 / 779,558). The formula used for this experiment is provided in Table 1.
    [0075] Preparation Procedure: The water was loaded into a three-necked round-bottom flask equipped with a heating blanket, temperature controller, reflux condenser and mechanical stirrer. Sodium bisulfite was added to the water at room temperature followed by the addition of the soy flour over a period of five minutes. The mixture was stirred for five minutes for homogeneity and then heated to 82 ° C denaturation temperature plus thirty minutes. The reaction was maintained at the fixed temperature +/- 1.0 ° C for one hour with stirring at which point the heat was removed and the urea was added to the heat-denatured soy and maintained for an additional 15 minutes with stirring. The addition of urea cooled the soy adhesive to 44 ° C. The reaction was further cooled to 25 ° C in an ice / water bath and stored for use in plastic bottles at room temperature.
    [0076] Table 1
    [0077] Formula for Example 2

    QC: pH = 6.91, Viscosity = 5320 cP (for # 5 spindle)
    [0078] Example 3. Adhesive denatured with acid - Soy / Urea = 1: 2 @ 54% Total Solids (12AU-54)
    [0079] The soy flour was denatured with acid and then combined with urea to produce a stable aqueous soy / urea product. The formula used for this experiment is provided in Table 2.
    [0080] Preparation Procedure: The water was loaded into a three-necked round-bottom flask equipped with a suspended mechanical stirrer. Sodium bisulfite was added to the water at room temperature followed by the addition of soy flour over a period of five minutes. The mixture was stirred for 30 minutes at room temperature (Viscosity = 2800 cP for RV # 5, pH = 6.03). The acid (50% sulfuric acid) was then added dropwise to the mixture with rapid stirring until a pH of 3.0 (referred to as the acid-denatured pH) was reached and subsequently maintained for an additional 30 minutes . Urea was then quickly added to the acid-denatured soy mixture with rapid stirring and allowed to stir for 5 minutes. The addition of urea cooled the soy adhesive; thus the adhesive was heated to 25 ° C with a water bath and stored for use in plastic bottles while remaining at room temperature. The product was a very homogeneous, light brown, creamy product that had a little foam present on the top.
    [0081] Table 2
    [0082] Formula for Example 3

    Final Properties: pH = 3.92, Viscosity = 2180 cP (spindle # 4)
    [0083] Example 4. Denatured adhesive with acid - Soy / Urea = 1: 2 @ 54% Total Solids (12AUB-54)
    [0084] To the resin produced in Example 3, base (50% NaOH) was added slowly to the adhesive with rapid stirring to increase the pH to 7.
    [0085] Table 3
    [0086] Formula for Example 4
    Final Properties: pH = 7.07, Viscosity = 1820 cP (spindle # 4)
    [0087] Discussion of Comparison of Example 4 and Example 2
    [0088] The products produced in examples 2 and 4 are very similar in composition. The 12AUB-54 (Example 4) of this invention is significantly lower in viscosity than Control Example 2. Both show excellent stability to pH over time indicating that the resins are significantly free of urea in both examples. The ability to produce such a product without the use of heat is a significant improvement in adhesive technology. In addition, the color of the 12AUB is much lighter than that of the control 12HU. Figures 1 and 2 (together with Tables 4 and 5) demonstrate the lower viscosity of Example 4 denatured with acid, as well as the excellent stability (both pH and viscosity) achieved by both processes. The excellent pH stability is indicative of a soy adhesive that is significantly free of urea. It should be noted that the initial decrease in viscosity observed with the resin of Example 4 (12AUB) can be attributed to a reduction in foaming observed over the first few days. Once the foaming was depleted, the viscosity was exceptionally stable and the viscosity was only 20% of the control example.
    [0089] Table 4
    [0090] pH and Viscosity of 12HU (Example 2)

    [0091] Table 5
    [0092] pH and Viscosity of 12AUB (Example 4)


    [0093] Example 5. Denatured Acid Adhesive - Soy / Urea = 1: 2 @ 60% Total Solids (12AUB-60)
    [0094] The acid denaturation process provides products that are significantly lower in viscosity than the heat denaturation previously used. This also takes into account products with higher final solids being produced. In this example, a 60% solids adhesive is prepared in a similar manner to that described in Examples 2 and 3. A similar 60% solids sample of the heat treated adhesive was so viscous that it could not be agitated. In this example, Advantage 357 was added to reduce the foaming tendency often seen when mixing soy flour. The acid-denatured pH for this example was 3.5.
    [0095] Table 6
    [0096] Formula for Example 5
    Final Properties: pH = 7.04, Viscosity = 2340 cP (spindle # 4)
    [0097] Example 6. Acid Denatured Adhesive - Soy / Urea = 1: 2 @ 60% Total Solids (12ABU-60)
    [0098] The order of addition of the urea or base has been shown to be significant in that it affects the final viscosity. In this example, an adhesive similar to that of Example 5 was produced, but in this example the base was added to the acid-denatured soy BEFORE urea. The acid-denatured pH for this example was 3.5.
    [0099] Table 7
    [00100] Formula for Example 6
    Final Properties: pH = 7.37, Viscosity = 1420 cP (spindle # 4)
    [00101] The comparison of Example 6 with Example 5 shows that when urea is added after the base, the final product will have an even lower viscosity; 1420 cP vs. 2340.
    [00102] Example 7. Denatured Adhesive with Acid - Soy / Urea = 1: 1 @ 50% Total Solids (11ABU-50)
    [00103] The ability to produce an adhesive with higher solid contents, compared to the traditional heat treatment process, also provides the luxury of producing adhesives that are higher in soybean content and lower in urea content. This can be beneficial in properties and performance. In this example, the soybean: urea ratio was increased to 1: 1.0. The process used was identical to that described in example 6. The pH denatured with acid for this example was 3.5.
    [00104] Table 8
    [00105] Formula for Example 7
    Final Properties: pH = 6.36, Viscosity = 7880 cP (spindle # 5)
    [00106] The pH and viscosity stability of Example 7 containing high soy content are shown in Figure 3 and Table 9. These results further demonstrate the excellent practicality and simplicity of this process to produce stable soy / urea adhesives that are significantly free from urea activity.
    [00107] Table 9
    [00108] pH and Viscosity of 11ABU-50 (Example 7)

    [00109] Example 8. Denatured Acid Adhesive - Soy / Urea = 1: 1 @ 40% Total Solids (11AU-40)
    [00110] In some formulations, very low viscosities and high soy content may be desirable. In addition, the need for a product with a lower pH may be required if certain sensitive base crosslinkers are selected. In this example a product with a lower solid content (40%) was prepared and the base step was eliminated. The process used was similar to that described in Example 3. The acid-denatured pH for this example was 3.0.
    [00111] Table 10
    [00112] Formula for Example 8
    Final Properties: pH = 3.51, Viscosity = 600 cP (spindle # 5)
    [00113] Incorporation of Adhesive Reticulation and Performance
    [00114] Examples 3 to 8 describe the process for producing new acid-denatured soy / urea adhesives. Examples 9 to 11 demonstrate the effectiveness of adding crosslinkers, PAE and pMDI respectfully to these adhesives to improve performance. Examples 12 to 17 demonstrate the adhesive strength of these acid-denatured soy / urea adhesives with and without the addition of crosslinking agent using the ABES wet and dry strength assessment described.
    [00115] Examples 9 to 11. Soy / urea adhesive denatured with acid combined with PAE or pMDI
    [00116] The crosslinking agent, PAE (CA-1300) or pMDI, was added in some dry parts of crosslinker to 100 parts of dry soy / urea adhesive at room temperature, with modest stirring in a 150 ml beaker using a instant mixing blade and a suspended stirrer. After the crosslinking agent was added, the mixture was allowed to stir for 1 to 5 minutes with modest stirring.
    [00117] Table 11
    [00118] Acid denatured soy / urea adhesives combined with crosslinking agents

    [00119] The viscosity stability of Example 9 was found to be excellent for several hours, as expected from the previous PAE-soy mixtures, and the viscosity stability of Examples 10 and 11 are shown in figure 4 and Table 12. The use of pMDI with a compatible aqueous system is expected to be very reactive and the viscosity stability shown in these examples is considered to be very acceptable for mixing and use applications. For heat denatured resins, similar to Example 2, the stability is less 5 minutes before complete gelation occurs.
    [00120] Table 12
    [00121] Viscosity stability of Example 10 (50-pMDI) and Example 11 (100-pMDI)

    [00122] Examples 12 to 17. Soy / urea adhesive denatured with acid combined with PAE and pMDI
    [00123] Table 13
    [00124] Strength of Adhesives w / and Crosslinking Agents w / o

    [00125] The results of Table 13 show that all the adhesives evaluated showed good to excellent dry bond strength. However, in all base adhesives, the addition of a crosslinker was required to provide any wet force observable by the ABES method. Interestingly, the addition of pMDI showed the greatest improvement in wet strength, perhaps due to a greater amount of crosslinker being added.
    [00126] The cure rate, as measured using the ABES force development procedure, shows the development of bond strength over time when subjected to heat in a press. Figure 5 (with data in Table 14) shows a comparison of Examples 12, 14 and 16. Examples 12 and 14 follow a similar trend, suggesting comparable reactivity between the two products, while example 16 shows the ability to produce adhesives higher levels containing soybeans with appreciably higher solids content (50% for the acid denatured process vs. 38% for the heat denatured process) and how this results in faster curing (strength after only 10 seconds of press time) of the thermoset adhesives being produced.
    [00127] Table 14
    [00128] ABES cure rate curves


    [00129] In Examples 18 to 20, adhesives were produced to manufacture chipboard panels. The panels produced are from Examples 21 and 22. The agglomerate panels of Examples 21 and 22 were produced following the "Agglomerate Procedure" described above. This demonstrates the usefulness of the technology.
    [00130] Example 18 - Comparative Product through "Heat Denaturation"
    [00131] The production of 11HU-30PAE was conducted as follows. The PAE used was CA1300. This was produced by the procedure previously described by Wescott (U.S. Application # 11 / 779,558).
    [00132] Table 15: Formula for Example 18

    [00133] The water was combined with TS-soy flour (toasted soy flour) in a three-necked round-neck flask with suspended agitation, thermocouple and condenser. The mixture was heated to 83 ± 1 ° C and maintained for 60 minutes. The reaction was then removed from the heat and urea was added, resulting in rapid cooling to 50 ° C. The mixture was maintained at 50 ° C for 15 minutes and then cooled to room temperature in an ice / water bath. PAE (CA1300) was then added and the mixture was stirred for 15 minutes and used immediately. The final adhesive had the following properties; pH: 6.17 Viscosity (RVT # 5 10RPM): 3200 cP
    [00134] Example 19 - Product denatured with acid
    [00135] The production of 11AU-30PAE was conducted as follows. The PAE used was CA1300.
    [00136] Table 16
    [00137] Formula for Example 19

    [00138] The water was combined with SMBS (viscosity modifier) and soy flour-90 (unroasted soy flour) in a metal beaker with sustained agitation. Sulfuric acid was added and the mixture was stirred for 30 minutes. Urea was added to the mixture, the product was stirred for 30 minutes. PAE (CA1300) was then added and the mixture was stirred for 15 minutes and used immediately. The final adhesive had the following properties: pH: 4.04 Viscosity (RVT # 5 10RPM); 6140 cP
    [00139] Example 20 - Undenatured product containing no urea (for use as the core resin)
    [00140] The production of 12G-20PAE was conducted as follows. The PAE used was CA1300. (Brady Reference- US Patent Application Serial Number 12 / 287,394).
    [00141] Table 17
    [00142] Formula for Example 20

    [00143] The water was combined with Soy Flour-20 (toasted soy flour) in a round-bottomed three-necked bottle with suspended agitation. The mixture was stirred for 30 minutes. PAE (CA1300) was then added and the mixture was stirred for 15 minutes and used immediately. The final adhesive had the following properties: pH: 6.08 Viscosity (RVT # 3 10RPM): 1850 cP
    [00144] Examples 21 and 22:
    [00145] Two laboratory agglomerate panels were produced and tested using the Agglomerate Procedure described above. The results are shown in Table 18. These panels used Example 18 or Example 19 as a face adhesive and Example 20 also used as a core adhesive. These panels showed excellent performance and fast curing characteristics. The panels showed excellent values for MOR and MOE and modest values for internal bonding (IB). MOR, typically dominated by the face adhesive, shows that the acid-treated product produces better properties (both strength and solids / viscosity) than the heat-denatured product, thus increasing the utility of the invention. In addition, the acid-treated product (Example 19) was significantly lighter in color. These panels are excellent prototypes of agglomerate without added formaldehyde (NAF) which have a great commercial practical nature.
    [00146] Table 18
    [00147] Results of the Agglomerate Panel
    Seconds after the core reaches 100 ° C
    [00148] Mixtures with PVAc (polyvinyl acetate)
    [00149] Example 23: Compatibility with PVAc-
    [00150] The 11AU samples were mixed with PVAc obtained from Franklin International (Columbus, OH). The type of PVAc used was Duracet 12. The samples were analyzed for viscosity, pH and any sign of interruption of the PVAc emulsion.
    [00151] Table 19
    [00152] Formula for Example 23 (11 AU)


    [00153] The water was combined with SMBS (viscosity modifier) and soy flour-90 (unroasted soy flour) in a metal beaker with sustained agitation. Sulfuric acid was added bringing the pH to 3.54 and the mixture was stirred for 30 minutes. Urea was added to the mixture, the product was stirred for 15 minutes. The final adhesive had the following properties: pH: 4.19 Viscosity (RVT # 5 10RPM); 2370 cP
    [00154] Example 24 - Mixtures with PVAc and 11 AU
    [00155] The mixtures were prepared by mixing 11 AU from Example 23 above with PVAc in varying ratios to show the compatibility of the two products. Four mixing levels were chosen to show the wide range of mixtures possible. In all cases, the PVAc was placed in a 200 ml beaker and 11 AU (Example 23) was added. The mixture was stirred for 1 min and viscosity / pH data was obtained. In addition, for all mixtures, the two components were highly compatible and showed no sign of separation, precipitation or decantation. Table 20 shows the data.
    [00156] Table 20
    [00157] Data for PVAc / 11 AU Mixtures


    [00158] It should be noted that the above description, attached figures and their descriptions are intended to be illustrative and not limiting of this invention. Many themes and variations of this invention will be suggested to a person skilled in this technique, in the light of disclosure. All such themes and variations are within this contemplation. For example, although this invention has been described in conjunction with the various exemplary modalities outlined above, several substantial alternatives, modifications, variations, improvements and / or equivalents, whether known or which are, or may be, currently unforeseen, may become evident to those having at least common skill in the technique. Various changes can be made without departing from the spirit and scope of the invention. Therefore, the invention is intended to cover all alternatives, modifications, variations, improvements and / or substantial equivalents known or later developed from these exemplary modalities.
    权利要求:
    Claims (18)
    [0001]
    1. Stable adhesive composition, characterized by the fact that it is comprised of urea and soy flour in water, in which the urea present in the soy flour was deactivated by an acid treatment, in which the acid treatment comprises reducing the pH of the flour. soy dispersed to less than 4.5 and more than 2.0 for a period of at least 1 minute before combining it with urea; wherein urea is present in the composition in an amount equivalent to a maximum of five parts of urea by weight for each part by weight of soy flour.
    [0002]
    2. Composition according to claim 1, characterized by the fact that it still comprises a crosslinking agent.
    [0003]
    Composition according to claim 2, characterized by the fact that the amount of the crosslinking agent in the composition is 0.1 to 80% solids based on the total adhesive dry weight.
    [0004]
    Composition according to claim 2, characterized by the fact that the crosslinking agent comprises a formaldehyde-free crosslinking agent selected from the group consisting of isocyanate, polyamine epichlorohydrin resin, polyamidoamine-epichlorohydrin resin, polyalkylene polyamine-epichlorohydrin , amine-epichlorohydrin polymer epoxy resin, aldehyde, aldehyde starch, dialdehyde starch, glyoxal, glyoxal urea, urea-aldehyde resin and mixtures thereof.
    [0005]
    Composition according to claim 2, characterized by the fact that the crosslinking agent comprises an isocyanate.
    [0006]
    A composition according to claim 2, characterized by the fact that the crosslinking agent comprises a polyamidoamine-epichlorohydrin resin.
    [0007]
    7. Composition according to claim 2, characterized by the fact that the crosslinking agent comprises a crosslinking agent containing formaldehyde selected from the group consisting of formaldehyde, phenol formaldehyde, melamine formaldehyde, urea formaldehyde, melamine urea formaldehyde, resorcinol formaldehyde phenol and any combination of these.
    [0008]
    8. Composition according to claim 1, characterized by the fact that it still comprises an emulsion polymer.
    [0009]
    Composition according to claim 8, characterized in that the amount of the emulsion polymer in the composition is 0.1 to 80% dry weight based on the total adhesive dry weight.
    [0010]
    Composition according to claim 8, characterized in that the emulsion polymer comprises a polyvinyl acetate (PVAc).
    [0011]
    11. Composition according to claim 1, characterized by the fact that it still comprises a diluent.
    [0012]
    12. Composition according to claim 11, characterized by the fact that the diluent is selected from the group consisting of glycerol, ethylene glycol, propylene glycol, neopentyl glycol and their polymer versions.
    [0013]
    13. Method of producing a stable adhesive composition as defined in claim 1, the method characterized by the fact that it comprises the steps of a) dispersing the soy flour in water b) reducing the pH of the dispersed soy flour to at least 4, 5, but greater than 2.0 for a period of at least 1 minute before combining with urea, thus deactivating urea, c) contacting dispersed soy flour with urea, and in which urea is added to the soy flour in an amount equivalent to a maximum of five parts of urea by weight for each part of soy flour.
    [0014]
    Method according to claim 13, characterized in that urea is added to the soy flour after the soy flour is substantially free from urea.
    [0015]
    Method according to claim 13, characterized in that it further comprises the addition of an emulsion polymer.
    [0016]
    16. Method according to claim 15, characterized in that the amount of the emulsion polymer added is 0.1 to 80% dry weight based on the dry weight of the total adhesive.
    [0017]
    17. Method according to claim 13, characterized in that it still comprises the step of adding a diluent.
    [0018]
    18. Method according to claim 13, characterized in that it still comprises the step of adding a crosslinking agent.
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    公开号 | 公开日
    EP2470337B1|2020-03-04|
    KR101640633B1|2016-07-18|
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    AU2010286553A1|2012-02-23|
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    法律状态:
    2018-02-06| B25A| Requested transfer of rights approved|Owner name: SOLENIS TECHNOLOGIES CAYMAN, L.P. (CH) |
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-19| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 13/10/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US23781309P| true| 2009-08-28|2009-08-28|
    US61/237,813|2009-08-28|
    PCT/US2010/046898|WO2011025911A1|2009-08-28|2010-08-27|Stable acid denatured soy/urea adhesives and methods of making same|
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