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    • 专利摘要:
    ADHESIVE ENHANCED WITH INSULATING PROPERTIES. The present invention relates to an improved adhesive composition having enhanced insulating properties. The adhesive composition having improved insulating properties includes a starch component, an alkaline component; sodium tetraborate; Water; and a plurality of expandable microspheres. Products having improved insulating capabilities and methods of producing products having improved insulating capabilities are also provided. The present sticker and products including the sticker are environmentally friendly.
    公开号:BR112013004955B1
    申请号:R112013004955-3
    申请日:2011-09-09
    公开日:2021-05-25
    发明作者:Tianjian Huang；Robert Sandilla；Daniel Waski
    申请人:Henkel IP & Holding GmbH；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to an adhesive composition having better insulating properties. In particular, the invention includes an adhesive composition and method of making an adhesive composition for use in providing insulation for paper products, including corrugated products. FUNDAMENTALS OF THE INVENTION
    [002] Cardboard, including corrugated cardboard, is commonly used to provide insulation for various products, including paper cups. Traditionally, corrugated board is prepared by first forming a corrugated element, or "medium", by passing a sheet of cellulose between the corrugating rolls forming a substantially sinusoidal or serpentine cross-section in the sheet. The ends of the sinusoidal portion are referred to as column splines. An adhesive is commonly applied to the ends of the flutes, and an uncurled or planar cellulosic liner is applied against the adhesive coated flutes of the corrugated elements when the corrugated sheet is passed between a curling roller and a pressure roller. A resulting paper product having the curling medium on one side and the planar liner on the other side is called a single sided fabric. The single sided element can be used as is in certain applications as a liner or buffer material within a container. In some products, adhesive is also applied to the column flute ends of the single sided fabric and a second backing sheet is subsequently applied to the fluted middle in a “double sided” operation. The second liner sheet is exposed to heat and pressure conditions during its contact with the adhesive. In practice, the most frequently encountered sheet of corrugated cardboard has two flat sides placed on each side of the corrugated medium. Depending on the specific strength desired, a sheet of corrugated board can also be provided with a more complex structure, such as two corrugated media and three flat surfaces, two outer surfaces and an inner surface that separates the two corrugated media.
    [003] Starch-based adhesives are most commonly used in the curling process due to their desirable adhesive properties, low cost and ease of preparation. The most fundamental starch curling adhesive, commonly referred to as a “Stein-Hall” formulation, is an alkaline adhesive comprising starch in a natural, non-gelatinized state suspended in an aqueous dispersion of cooked starch. The adhesive is produced by gelatinizing starch in water with sodium hydroxide (caustic soda) to produce a primary blend of gelatinized or cooked carrier, which is then slowly added to a secondary blend of raw starch (non-gelatinized), borax and water to produce the fully formulated adhesive. In conventional corrugating processes, the adhesive is applied to the middle ends of fluted paper or single-sided cardboard, after which the application of heat and pressure motivates the starch in its natural state to gelatinize, resulting in an instantaneous increase in viscosity and formation of the adhesive bond.
    [004] Although typical adhesives are sufficient to adhere the various layers of insulating paper to each other, these adhesives do not act as insulators by themselves. Thus, in typical situations, at least two layers of paper (the lining and the middle) are required, and in many situations three layers are required (two linings and the middle). To achieve proper insulation, typical insulating products require the medium to have a reasonably high amplitude in its wave pattern, which requires more role to be used in shaping the medium. These typical formulations result in a tremendous amount of paper to be used for the product, which not only adds cost to production but is also not environmentally sound.
    [005] The present invention seeks to improve insulation papers, through the use of an adhesive composition that adds insulating properties to the product. Furthermore, the adhesive and products produced from it are manufactured from natural components and are environmentally conscious. The present invention provides an environmentally healthy insulating adhesive that provides sufficient adhesion to the product to which it is applied. SUMMARY OF THE INVENTION
    [006] The present invention relates to a starch composition and method of using the starch composition, which provides greater insulation while maintaining sufficient adhesive strength. The present invention balances the curing properties of the starch composition with the expansion properties of an insulating component to provide a suitable adhesive. In particular, the starch composition is selected to have gelatinization and curing temperatures, which also allow for sufficient expansion of the insulating component to maximize the benefits of both adhesive strength and insulating properties.
    [007] In a first embodiment of the present invention, an adhesive composition having better insulating properties is provided, including a starch component; an alkaline component; sodium tetraborate; Water; and a plurality of expandable microspheres, where the starch component is selected to allow complete gelatinization of the starch component at a temperature equal to or greater than the temperature at which the expandable microspheres expand.
    [008] Another embodiment of the invention provides a method of preparing a corrugated product having improved insulating properties, including the steps of: providing a substantially flat paper liner having a first side and a second side; providing a paper liner having a plurality of flutes each having a ridge and a depression; preparing an adhesive composition having better insulating properties, including the steps of: combining the high amylose starch component, an alkaline component, a crosslinker, and water to form a starch mixture, and then cooking the high starch mixture amylose content to form a cooked starch mixture; adding an unmodified starch component to the cooked starch mixture; and adding a plurality of expandable microspheres to the cooked starch mixture; applying the adhesive composition to one end of each of the flutes; matching the ridges of said ridges with a surface of the first side of the planar paper liner to form a composite structure where the first paper liner and the second paper liner come into contact with each other at the ridges of the ridges; cure the adhesive composition on the composite structure at a first temperature and a second temperature, where the first temperature and the second temperature differ by about 20°F (-6.7oC) to about 40°F (4.4oC).
    [009] Yet another embodiment of the invention provides a method of manufacturing an insulating sheet, including the steps of: providing a substantially flat sheet of paper having a first side and a second side, the first side having a surface with sufficient structure to accommodate an insulating component; preparing an adhesive composition which includes the steps of: combining the high amylose starch component, an alkaline component, a crosslinker, and water to form a starch blend and then cooking the high amylose starch blend to form a cooked starch mixture; adding an unmodified starch component to the cooked starch mixture; and adding a plurality of expandable microspheres to the cooked starch mixture; applying the adhesive composition to the first side of the substantially flat sheet of paper to form a sheet with an adhesive composition applied; heating the sheet with an applied adhesive composition to a first temperature sufficient to expand the expandable microspheres; and heating the sheet with an applied adhesive composition to a second temperature sufficient to fully cure the adhesive composition. BRIEF DESCRIPTION OF THE FIGURES
    [0010] Figure 1 represents the results of the test conducted with various adhesives, demonstrating the adhesion compared to the expansion of the microspheres. Represents Dualite graduations at maximum expansion.
    [0011] Figure 1A is a modality of a mechanism for manufacturing corrugated cardboard. Represents a single-sided corrugator application scheme.
    [0012] Figure 2 is an approximate cross-sectional view of a corrugated board that does not include expandable microspheres.
    [0013] Figure 3 is an approximate cross-sectional view of a corrugated board that includes expandable microspheres.
    [0014] Figure 4 is an approximate cross-sectional view of a corrugated board that includes expandable microspheres. DETAILED DESCRIPTION OF THE INVENTION
    [0015] Typical adhesives for use in insulating paper products provide negligible, if any, insulation properties to the final product. These adhesives are generally only useful for adhering a liner (or liners) to the middle, allowing air space between the edge of the flute and the liner to achieve insulation. Furthermore, since the adhesive composition only provides adhesion between the edge of the flute and the liner, there is very little space between the edge of the flute and the liner at the point of adhesion. The lack of space between these two elements at the tack point provides very little added insulation, if any. Since air is the main insulating medium, the amplitude of the waveforming of the medium must be significant, which requires the medium to be produced from a sheet of paper that is very large. In addition, to provide sufficient insulation, such typical products generally use thick layers of paper to form the liner(s), or alternatively use multiple layers of paper, to form a liner. As a result, the typical processing of such products is not only an expensive manufacturing process, but it also results in a large amount of waste.
    [0016] The present invention provides an adhesive composition that provides insulating properties to the product on which it is used. The adhesive compositions described herein may be useful in traditional corrugated board products having a middle and one or two liners. Through the use of the adhesive composition of the invention, greater insulating space can be provided between the end of the middle flute and the liner to which it is attached at the tack point. In alternative embodiments, the adhesive composition of the invention may be useful in forming a cardboard insulation that avoids the need for a medium, rather than relying on the adhesive composition itself to provide the desired insulation. The adhesive composition described herein is substantially produced from natural biodegradable materials, and products made with the adhesive composition of the invention require less paper to form. The end result is a cheaper and more environmentally conscious product. Insulating products useful in this document include paper products for household use, such as for hot beverage cups, hot food containers, and the like.
    [0017] The present invention is based on the discovery that an adhesive composition for use in the preparation of insulation products can include a plurality of expandable microspheres within it. When these expandable microspheres are allowed to expand into an adhesive composition, they create a foam-like adhesive material that provides additional insulation to the product. For example, when adhesive is applied between the liner and the end of a media flute, the expandable microspheres can be expanded, thus providing an insulating space between the end of the flute and the liner at the point of attachment. This insulated space adds insulating properties to the formed product, which allows for a medium having a smaller amplitude between the waves to be used (ie, it requires less air space), and provides even more adequate insulation. The media layer can have a flatter wave configuration, resulting in less paper used in the media. Additionally, the additional insulation allows the product to use thinner paper and/or single-layer paper liners, which results in lower costs and less wasted materials.
    [0018] In a first embodiment, the invention includes an adhesive for the preparation of an insulating cardboard, such as corrugated or uncorrugated cardboard. Cardboard can be produced from any type of paper material, including cellulosic paper materials traditionally used in insulating products. Desirably, the paper products used are recyclable materials.
    [0019] The adhesive composition can be prepared from any number of materials. Desirably, the adhesive composition includes water, a starch component, a crosslinking component, an alkaline component, and a plurality of expandable microspheres. The adhesive composition can further include one or more wetting agents, preservatives, or fillers. Other materials that do not adversely affect the adhesive and insulating properties of the adhesive composition can be used as desired.
    [0020] The adhesive composition may include any polar solvent, particularly water, in the formulation. In a desired embodiment, prior to setting (or gelatinizing) the composition, the adhesive composition includes the polar solvent in an amount of from about 40% to about 75% by weight of the adhesive composition prior to setting the composition, and more desirably of about 50% to about 70% by weight of the composition prior to setting the composition.
    [0021] The adhesive composition includes a starch component. The starch component can be present in the adhesive composition in any amount, and desirably is present in an amount of between about 20% to about 40% by weight of the adhesive composition prior to setting the composition, and more desirably about 25 % to about 35% by weight of the adhesive composition prior to setting the composition. The starch component can include any desired starch materials, in particular starch materials derived from natural sources, including, for example, corn. In some embodiments, the starch component can include starch having a highly branched composition. For example, the starch component can include unmodified starch, or "granulated" starch. As used herein, the term "unmodified" starch refers to a starch composition having less than 25% amylose content. Unmodified starch can be used in any form, and is preferably used in powder or granular form having a diameter of about 20 microns. In other embodiments, the starch component can include a cooked starch, also referred to as a carrier starch. Cooked starch can have a higher viscosity than unmodified starch.
    [0022] In yet other embodiments, the starch component may include a starch material that has a composition with a higher concentration of straight chain materials. Such components may include a high amylose starch material, including that sold by Henkel Corporation under the trade name Optamyl®. As used herein, a starch having a high amylose content (referred to as "high amylose starch") includes at least 50% amylose content. In some embodiments, a high amylose starch can have between about 25% to about 50% amylose, and more desirably between about 35% and 50% amylose concentration. As will be explained below, in one embodiment, the use of a high amylose starch material in combination with an unmodified starch material can be beneficial for the expansion of the microspheres in the adhesive composition. The combination of high amylose starch and unmodified starch results in a starch component that has a higher moisture content and a higher final setting (or curing) temperature.
    [0023] In embodiments where the starch component includes a combination of materials, the starch component includes a mixture of unmodified starch and at least one of cooked starch or high amylose starch. Desirably, the starch component includes a mixture of unmodified starch and high amylose starch. The unmodified starch component can be from about 60% to about 90% by weight of the starch component. In preferred embodiments, the unmodified starch component and the high amylose starch component are present in a ratio of from about 5:1 to about 3:1.
    [0024] The adhesive composition may include one or more alkaline components. The alkaline component can be present in an amount of from about 0.5% to about 1.5% by weight of the adhesive composition prior to setting the composition. The alkaline component can include any component having an alkaline nature. In particular embodiments, the alkaline component includes sodium hydroxide, however, any desired alkaline component may be used as desired.
    [0025] The adhesive composition may include one or more crosslinking components. Crosslinkers useful in the present invention can include, for example, sodium tetraborate (also referred to as borax). Crosslinkers may be present in the present invention in an amount of from about 0.10% to about 0.20% by weight of the adhesive composition prior to setting the composition.
    [0026] The adhesive composition can include any optional components, including humectants, preservatives, or fillers. Humectants useful in the present invention aid in maintaining the viscosity stability of the composition, and may include, for example, glycerol, glycerin, urea, propylene glycol, glyceryl triacetate, sugars and sugar polyols such as sorbitol, xylitol, and maltitol, polymeric polyols such as polydextrose, natural extracts such as quillaia or lactic acid, or any other desired composition having wetting properties. Humectants may be useful in the present invention in an amount of from about 0.1% to about 15% by weight of the adhesive composition prior to setting the composition. Preservatives may be useful in the present invention, and include preservatives such as 1,2-benzisothiazolin-3-one. Preservatives can be used in the amount of from about 0.05% to about 0.20% by weight of the adhesive composition prior to setting the composition. Any desirable fillers can be used as are known in the art.
    [0027] The adhesive composition includes a plurality of expandable microspheres. The expandable microspheres useful in the present invention must be capable of expanding in size in the presence of heat and/or radiant energy (including, for example, microwave, infrared, radio frequency, and/or ultrasonic energy). Microspheres useful in the present invention include, for example, heat-swellable polymeric microspheres, including those having a hydrocarbon core and a polyacrylonitrile structure (such as those sold under the trade name Dualite®) and other similar microspheres (such as those sold under the trade name Expancel®). The expandable microspheres can be any unexpanded size, including from about 12 microns to about 30 microns in diameter. In the presence of heat, the expandable microspheres of the present invention may be capable of increasing in diameter from about 3 times to about 10 times. That is, the diameter of the expandable microspheres can be expandable from around 300% of the starting diameter to about 1000% of the starting material, and more desirably, the diameter of the expandable microspheres can be expandable from about 350% to about 600% the starting diameter. Upon expansion of the microspheres in the adhesive composition, the adhesive composition becomes a foam-like material, which has improved insulation properties. It may be desirable, as will be explained below, that expansion of the microspheres takes place in a partially gelatinized adhesive composition.
    [0028] The expandable microspheres have a specific temperature at which they begin to expand and a second temperature at which they have reached maximum expansion. Desirably, the temperature at which these microspheres begin to expand (Texp) is from about 180°F (82°C) to about 210°F (99°C), and more desirably from about 190°F (88°C) to about 208°F (98°C). The temperature at which the microspheres reached maximum expansion (Tmax) is desirably from about 250°F (121°C) to about 285°F (141°C), and more desirably from about 257°F (125°C) to about 275 °F (135°C). Of course, different grades of microspheres have different Texp and Tmax. For example, a particularly useful microsphere has a Texp of about 208°F (98°C) and a Tmax of about 275°F (135°C), while another useful microsphere has a Texp of about 190°F (88°C) and a Tmax of about 266°F (130°C). Although any particular grade of microspheres can be used in the present invention, the process should be modified slightly to account for the Texp and Tmax of the microspheres.
    [0029] Although the choice of particular microspheres and their respective Texp and Tmax is not critical to the invention, processing temperatures can be modified depending on these temperatures. In most applications, it is desirable for the Tmax for the microspheres to be a temperature that is equal to or less than the full setting (or curing) temperature of the starch adhesive composition. As can be seen by those of skill in the art, the adhesive composition of the invention includes a plurality of unexpanded microspheres in a fluid starch-based adhesive composition. Before the adhesive composition is fully fixed or cured, these microspheres are able to move within the composition and are able to expand. Once the adhesive composition is defined, however, the microspheres are substantially locked in place, making expansion difficult, if not impossible. For this reason, it is useful for the maximum expansion temperature of the microspheres (Tmax) to be equal to or lower than the full setting temperature of the adhesive composition.
    [0030] Of course, it can be seen that the starch-based adhesive composition will start to set, or gelatinize, at a temperature lower than the full cure temperature. In some embodiments, the initial setting temperature of the starch composition can be from about 138°F (59°C) to about 156°F (69°C). Although the starch adhesive begins to gelatinize at this temperature, the adhesive composition may still have a high moisture content and will be substantially liquid. The temperature at which the starch adhesive composition fully sets is desirably equal to or greater than the Tmax of the expandable microspheres, however, the temperature at which the starch adhesive composition fully sets may be between the Tmax and Texp of the microspheres .
    [0031] It may be desirable that the maximum expansion temperature of the microspheres (Tmax) and the final setting temperature of the adhesive composition are different by about 20°F (-6.6oC) to about 40°F (4.4oC ), and most desirably around 30°F (-1.1oC). This difference takes into account the expandable microspheres to be expanded and the adhesive to be properly fixed. Desirably, the temperature at which the adhesive begins to gelatinize can be from about 20°F (-6.6°C) to about 40°F (4.4°C) lower than the Texp of microspheres, and more desirably around 30°F (-1.1oC) lower than the Texp of microspheres, and the temperature at which the adhesive is fully set can be from about 20°F (-6.6oC) to about 40°F ( 4.4oC) higher than the Tmax of microspheres, and desirably around 30°F (-1.1oC) higher than the Tmax of microspheres.
    [0032] In a particularly desirable embodiment of manufacturing products, the adhesive composition can be applied to the surface (or surfaces) of a product and subjected to sufficient heat to begin gelatinization of the adhesive. Beginning gelatinization of the adhesive can help hold the adhesive and microspheres in place, but will allow the microspheres the freedom to expand. The heat can then be raised to a temperature sufficient to expand the microspheres. Finally, the heat can be raised again to a temperature sufficient to completely set the adhesive composition. Heat can be applied by any desirable method, which includes an oven or through the use of heated rollers. It should be noted that the various stages (beginning of gelatinization, expansion of the microspheres, and complete fixation of the adhesive) can be achieved through radiation energy, as a substitute for or in addition to direct heat. That is, for example, the various steps can be achieved through the use of microwaves or radio frequency radiation, for example. In addition, the process can include any combination of applying heat and applying radiation. For example, the start of gelatinization of the adhesive composition can be achieved by means of direct heat, while the expansion of the microspheres can be achieved through the application of radiation energy.
    [0033] In some embodiments, the starch component of the adhesive composition includes a combination of unmodified starch and high amylose starch. This combination of starches results in a composition having a higher moisture content, and thus a higher final setting temperature. Although the beginning of the adhesive gelation temperature may remain around the same temperature, the final setting temperature may be higher than with unmodified starch alone. The present inventors have found that, by increasing the setting temperature of the adhesive composition, a greater temperature gap can be provided at which the microspheres expand. Other additives can be included in the composition to increase the setting temperature of the adhesive as desired.
    [0034] The adhesive composition includes a plurality of unconsumed expandable microspheres. Depending on the particular expandable microspheres used in the composition, the desired amount of microspheres in the composition can be modified. It has been discovered by the present inventors that if the adhesive composition includes a very high concentration of expandable microspheres, there will be insufficient adhesion after expansion of the microspheres. However, if it is not a very low concentration of expandable microspheres, there will be insufficient expansion of the resulting adhesive and thus insufficient insulation. Therefore, examination of the charge level and expansion ratio, as well as the expansion ratio and temperature at the charge level, must be taken into account when determining the optimal concentration of expandable microspheres in the composition. If the expansion ratio of the microspheres is lower, there may be a higher concentration in the adhesive composition, and conversely, if the expansion ratio of the microspheres is higher, there may be a lower concentration of the adhesive composition.
    In preferred embodiments, it is desirable that the expandable microspheres are present in the adhesive composition in an amount of from about 0.5% to about 5.0% by weight of the adhesive composition prior to setting the composition, and more desirably of about 1.0% to about 2.0% by weight of the adhesive composition before setting the composition, and most desirable around 1.2% by weight of the adhesive composition before setting the composition. For an embodiment including expandable microspheres having a diameter expansion ratio of about 370% at Tmax, the microspheres may be present in an amount of from about 1.5% to about 2.0% by weight of the adhesive composition before of fixing the composition. For an embodiment that includes expandable microspheres that have a diameter expansion ratio of around 470% at Tmax, the microspheres may be present in an amount of from about 1.0% to about 1.5% by weight of the composition. adhesive before fixing the composition. In systems where less heating capabilities exist, it may be desirable to include a higher concentration of expandable microspheres, such as up to 4% by weight of the adhesive composition prior to setting the composition. The expansion ratio of the expandable microspheres and the charge level of the microspheres will be related to each other. As shown in Figure 1, the Applicant has tested several different grades of expandable microspheres, demonstrating the concentration of microspheres in various adhesive compositions that fall within the "danger zone" (loss of adhesion) and the "safe zone" (good adhesion). Desirably, the concentration of microspheres in the adhesive composition should lie between these two zones. This balances expansion, and thus insulation, with the resulting foam-like adhesive adhesion.
    [0036] The present invention provides a method of preparing an adhesive composition having improved insulation properties. The method includes first combining a starch component, alkaline component, crosslinkers, polar solvent, and optional wetting agents, preservatives or fillers to form a starch mixture. Once the starch mixture is formed, it can be partially gelatinized to form a gelatinized starch mixture, and then the plurality of expandable microspheres can be added to the gelatinized starch mixture. If desired, the plurality of expandable microspheres can be added to the starch mixture prior to commencing gelatinization. In some embodiments, the starch component can include a combination of unmodified starch and high amylose starch. In such embodiments, it may be preferable to combine the high amylose starch component, alkaline component, crosslinker, polar solvent and optional wetting agents, preservatives and fillers, gelatinize this mixture, and then separately add the non-starch component. modified. Once this mixture is obtained, the plurality of expandable microspheres can be added.
    [0037] In other embodiments, the present invention provides a kit for providing an adhesive composition having improved insulation properties. In this embodiment, the kit includes two parts, a first part and a second part, which are desirably stored in separate containers. The first part includes a starch adhesive component, including the starch component, the alkaline component, the crosslinker, the polar solvent and optional wetting agents, preservatives or fillers. The first part can be partially gelatinized, if desired, which provides greater viscosity to the first part. The second component includes the plurality of expandable microspheres. The second part can include the microspheres in any form such as dry powder, suspension or any other desired shape. The kit may further include a means for combining the two parts together to form the adhesive composition having improved insulating properties, such as a separate container into which each of the first and second parts can be fed. If desired, the kit can further include instructions for use in preparing the adhesive composition.
    [0038] The present invention is further related to an insulated corrugated board. Any known process for forming corrugated board can be used, and Figure 1A represents one embodiment of an assembly useful in forming corrugated board. Desirably, the cardboard is produced from paper that has a reduced thickness compared to traditional corrugated insulating cardboards. Any type of paper can be used in the invention, for example, the paper can be from about 0.0036 inches thick to about 0.0052 inches thick. Furthermore, it is desirable to use lighter weight paper than that which is traditionally used in insulation products. Traditional insulation products generally use “33#” paper for the various paper components. It is desirable to use paper that is of a lighter weight than "23#" paper, and more desirably it is desirable to use "18#" paper for the various components of the corrugated board. That is, the various components (including liner and media) desirably include paper which is known as 18# paper (0.0036 inches thick, density about 67.72 g/m2).
    [0039] Insulated corrugated cardboard can be single-sided or double-sided. Single sided corrugated boards include a single paper liner, which is a substantially flat paper liner having a first side and a second side, and a middle, which is a paper liner having a first side and a second side that has been formed in a sine wave configuration that has a plurality of ridges on each side. In this embodiment, the first side of the paper backing is secured to the ends of the flutes on the middle first side. A double-sided corrugated board further includes a second paper liner, which is a substantially flat paper liner having a first side and a second side, where the first side of the second paper liner is secured at the ends of the flutes on the second side of the quite. Although the description below of cardboard and the methods for manufacturing such cardboards are generally directed towards single-sided cardboards, it is to be understood that the invention still relates to double-sided cardboards, which can be obtained by including a second lining in the processing time of the first lining or after the first lining has been adhered.
    [0040] The inventive corrugated board of the present invention includes the adhesive of the invention described above. The adhesive of the invention, including the starch component, the alkaline component, the crosslinker, the polar solvent, the plurality of expandable microspheres, and optional wetting agents, preservatives, or fillers, is applied to the ends of the middle ridges. In an embodiment of the invention, including a high amylose starch component and an unmodified starch component, the high amylose starch component, an alkaline component, a crosslinker and water are combined to form a starch mixture. , and then the high amylose starch mixture is cooked to form a cooked starch mixture. Shortly thereafter, an unmodified starch component can be added to the cooked starch mixture, and a plurality of expandable microspheres are added to the cooked starch mixture. Alternatively, the adhesive components can simply be added together.
    [0041] If a single-sided corrugated board is desired, the adhesive composition is applied to the ends of the flutes on only one middle side, and the first side of a paper backing is applied over this. If desired, the adhesive composition is partially gelatinized. The expandable microspheres are allowed to expand and then the adhesive composition is placed in place. The resulting corrugated board has an insulating space between the surface of the paper backing and the ends of the middle flutes at the point of adhesion. Corrugated board desirably has an insulating space between the paper backing and the ends of the flutes at the tack point in the amount of about 0.01 inch. It should be understood, of course, that the particular increase in distance between the ends of the flute and the liner is not critical, and that a small increase in distance can generate a significant amount of additional insulation. In desired embodiments, the space between the end of the flute and the release liner in the present invention can be greater than the distance between the end of the flute and the liner without expanded materials. At the same time, the desired increase in the distance between the end of the flute and the liner should not be so great as to be detrimental to the strength of the bond between the two.
    [0042] If a double-sided corrugated board is desirable, the adhesive composition is applied to the ends of the second middle side flutes, and a second paper liner is applied. Similarly, the adhesive is partially gelatinized, the expandable microspheres are allowed to expand and then the adhesive composition is placed in place. The resulting corrugated board has an insulating space between the surface of the paper backing and the ends of the middle flutes. Corrugated board desirably has an insulating space between the paper backing and the ends of the flutes at the tack point in an amount that is greater than the space traditionally seen with conventional adhesives. In one embodiment, the increase in space between the two generated by the expanded microspheres is about 0.001 inch.
    [0043] The present invention is not limited to single or double-sided corrugated board, and can be used in various applications. Other applications in which the invention is useful include higher viscosity double reverse wave formulations, low viscosity coating applications, and the like.
    [0044] It is particularly preferable that the middle layer has a reduced amplitude compared to traditional corrugated boards. Through the use of the present invention, there is an insulating space between the end of the flute and the liner surface at the contact point, which provides additional insulation. This additional insulation reduces the need for so much air space between the flutes on the second side of the middle and the paper backing. In a preferred embodiment, the amplitude of the medium is about 0.04 inches as measured from the end of adjacent ridges, whereas traditional means have a ridge wavelength of from 0.063 to about 0.134. Thus, in one embodiment, the invention provides a corrugated board having a medium having a reduced wavelength, where the reduced wavelength is about 0.02 to about 0.09 inches less than traditional corrugated boards.
    [0045] It has been found that through the use of the present adhesive composition, and reducing the amplitude of the medium reduces the total amount of paper used in the corrugated board by about 20% compared to traditional corrugated boards. Furthermore, the additional insulation allows for insulation products to be formed with thinner paper and media backings, again resulting in reduced costs and also reduced waste.
    [0046] The present invention further provides a method of forming a corrugated board having better insulating properties. As explained above, the present inventors have found that the adhesive composition must balance the setting temperature of the starch-based adhesive with the expansion temperature of the expandable microspheres used therein. In the method of the invention, a first substantially flat paper liner having a first and a second side is provided. The first paper liner is about the same thickness as paper, it can be from about 0.0036 inches thick to about 0.0052 inches thick, which is thinner than traditional paper liners used in corrugated boards , which traditionally have a thickness of around 0.0062 inches. A second paper liner having a first and a second side is provided which is formed in a medium having a sine wave including a series of flutes on each of the first and second sides. The medium desirably has an amplitude of about 0.04 inches as measured from the end of adjacent flutes, and a wavelength of about 0.13 inches.
    [0047] An adhesive composition is prepared. The adhesive composition can be prepared just before the formation of the corrugated board or it can be prepared in advance and stored until needed. The adhesive composition is prepared by combining a starch component, alkaline component, crosslinker, polar solvent and optional wetting agents, preservatives or fillers to form a starch mixture, and partially gelatinizing the starch mixture to form a gelatinized mixture. A plurality of expandable microspheres are added to the gelatinized mixture, forming the adhesive composition. If desired, the expandable microspheres can be added to the starch mixture prior to partially gelatinizing the mixture.
    [0048] As explained above, the starch component of the adhesive composition may include an unmodified starch, cooked starch, high amylose starch, and combinations thereof. The various components of the adhesive composition can be present in the adhesive composition in the amounts described above. In preferred embodiments, the starch component includes a mixture of unmodified starch and high amylose starch. It is particularly preferable that the maximum expansion temperature of the microspheres is a temperature that is lower than the final setting temperature of the adhesive composition, for the reasons given above. However, the temperature at which the adhesive composition begins to gel or set may be lower than the expansion temperature of the expandable microspheres. If desired, additives or other components can be added to the adhesive composition to increase its setting temperature. It is desirable that the total adhesive set temperature be at least as high as the Tmax of the expandable microspheres, and particularly desirable that the total adhesive set temperature be at least 30°F (-1.1°C) higher than the Tmax of expandable microspheres.
    [0049] In the method of forming the corrugated board, a predetermined amount of adhesive composition is applied to the ends of the flutes on the first side of the middle. Desirably, the adhesive composition is applied in a relatively thin layer, the layer having a thickness of from about 0.05 to about 0.07 inches. The adhesive composition can be applied in the presence of heat and/or pressure. In one embodiment, the adhesive composition can be applied under a pressure of about 30 bar and when the medium is heated to a temperature of around 300°F (149°C).
    [0050] After the adhesive composition has been applied to the ends of the ridges on the first middle side, the ends of the ridges are brought into contact with the first side of the first paper liner. It is desirable that the contact be carried out under light pressure in order to effectively bond to the medium and the paper liner, but excess pressure should be avoided (to avoid compressing the adhesive from the point of contact) . At this point, an uncured corrugated product is formed, where the paper backing and the medium are held together through the adhesive, but the adhesive has not been fixed. If desired, the uncured corrugated product may be exposed to heat and/or radiation energy sufficient to begin gelatinization of the adhesive, but insufficient to expand the plurality of expandable microspheres. Gelatinizing the adhesive can be helpful in holding the various components of the product in place until final curing is established.
    [0051] The uncured corrugated product is then exposed to heat (including in an oven or through contact with heated rollers) and/or radiation energy (including, for example, microwave, infrared, radio frequency or ultrasonic energy) to expand the plurality of microspheres. In one embodiment, the uncured corrugated product is exposed to heat at a temperature sufficient to expand at least most of the microspheres at the end of a flute, but the temperature is insufficient to fully set the adhesive composition. In another embodiment, the uncured corrugated product is exposed to sufficient microwave or infrared energy to expand at least most of the expandable microspheres, but at an energy level that will not fully set the adhesive composition. The resulting product is an uncured corrugated product having expanded microspheres.
    [0052] As can be understood, at this point in the process, the microspheres at any given flute end have expanded to form a foam-like adhesive composition, which generates an increased space between the flute end and the paper liner. Thus, during the manufacturing process, it is important that the adhesive composition is allowed to expand and separate the first paper liner and the medium. That is, any pressure that maintains the first paper liner and the medium should not be so great as to prohibit expansion of the adhesive and thus separation of the paper liner and the medium. If the pressure is too great, the adhesive may expand to the side, that is, into the air space between the media and the paper backing. Furthermore, any heat and/or radiation energy applied to the product should not be so great as to completely fix the adhesive composition, allowing the microspheres to expand. It is desirable for the expanded adhesive composition to be located at each of the flute ends at the point of contact with the liner, thus providing insulating space between the first paper liner and the medium at the contact site.
    [0053] After expansion of the microspheres, the uncured corrugated product having expanded microspheres can then be exposed to heat and/or radiation energy (including microwave or infrared energy) sufficient to fully fix or cure the adhesive composition. The result is a corrugated paper having better insulating properties.
    [0054] The method described above provides a single-sided corrugated board. However, the above method can still be used to provide a double-sided corrugated board. In addition to the above steps, a second substantially flat paper liner can be provided. The second liner can be applied to the second side of the middle at the same time as the first liner is applied to the first side of the middle, or the second liner can be applied to the second side of the middle after the first liner has been adhered to the middle. It may be desirable for the second liner to be applied to the second side of the middle after the first liner has fully adhered to the middle. The processing and fixing steps as described above can be repeated with the second liner to provide a double-sided corrugated board.
    [0055] In some embodiments, it may be desirable to form recesses of expanded adhesive material (also referred to as "fillets") along the sides of the flute ends, between the flute and the liner. For example, as can be seen in Figure 2, which is a close-up cross-sectional view of a corrugated board bonded without expandable microspheres, there is little material on the sides of the flute edge. Figures 3 and 4, however, are approximate cross-sectional views of a corrugated board adhered with expandable microspheres, which represent the presence of expanded adhesive composition on the sides of the flute. These recesses can aid in the strength of the bond between the medium and the liner, and can therefore be desirably generated. However, it is naturally understood that the formation of undercuts alongside the streaks is not necessary and may not, in some embodiments, be desired.
    [0056] In an alternative embodiment, an insulating paper product that has no media is provided, and a method for forming an insulating paper product that has no media. As can be seen by those of skill in the art, conventional corrugated insulating boards require the presence of the medium, which has a sine wave configuration to provide an air gap between the medium and the paper backing. Air bags provide the necessary insulation. Since the middle layer constitutes more than half the paper of the corrugated product in a single-sided design, it would be particularly desirable for the middle layer to be omitted. Removal of the medium should result in a product that uses less than half of the paper traditionally required, which would significantly reduce the cost associated with the product and also reduce waste generated by more than half. However, until now, it has been difficult to get a product that has the necessary insulation without including the middle layer.
    [0057] The present invention provides an insulating product that does not include a layer of media. It has been found that the adhesive composition of the present invention is capable of providing the necessary insulation required in insulating products. In this embodiment, an insulation sheet is provided that includes a substantially flat paper liner having a first side and a second side. The first side of the paper liner includes a plurality of expandable microspheres secured in an adhesive composition, where the plurality of expandable microspheres has been expanded and the adhesive composition has been fixed or cured. Thus, the product includes a paper liner having a foam-like composition adhered to its first side. The expandable microspheres include those described above, and the adhesive composition includes the components described above, including the starch component, the alkaline component, the crosslinker, the polar solvent, and optional wetting agents, preservatives or fillers. As explained above, the starch component of the adhesive composition can include an unmodified starch, cooked starch, high amylose starch, and combinations thereof.
    [0058] The adhesive composition of the insulating product can be applied to the first surface of the paper liner in any desired configuration, including in a series of dots, stripes, waves, checkerboard patterns, any general forms of polyhedron that have substantially bases planes, and their combinations. In addition, the adhesive composition can be applied to the first surface in a series of rollers. In addition, if desired, the adhesive composition can be applied to the first surface as a substantially flat sheet of adhesive that covers the entire first surface or that covers a portion of the first surface. Optionally, a second paper liner can be applied to the top surface of the adhesive composition, forming an intercalated configuration of: first paper liner - adhesive with expanded microspheres - second paper liner.
    [0059] A method of forming an insulating sheet is also provided. In this method, a substantially flat paper liner having a first surface and a second surface is first provided. An adhesive composition is prepared. The adhesive composition can be prepared just before the formation of the insulating sheet, or it can be prepared in advance and stored until needed. The adhesive composition is prepared by combining the materials described above, including a starch component, the alkaline component, crosslinker, polar solvent, and optional humectants, preservatives or fillers, to form a starch mixture, and gelatinize the starch mixture to form a gelatinized mixture. In embodiments where the starch component includes a combination of unmodified starch and a high amylose starch component, it may be desirable to partially gelatinize the high amylose starch component, the alkaline component, the crosslinkers, the plain solvent, and the optional wetting agents, preservatives and fillers prior to addition of the unmodified starch component. A plurality of expandable microspheres are added to the partially gelatinized mixture, which forms the adhesive composition. If desired, the expandable microspheres can be added to the starch mixture before partially gelatinizing the mixture.
    [0060] As explained above, the starch component of the adhesive composition may include an unmodified starch, cooked starch, high amylose starch, and combinations thereof. The starch component desirably includes the mixture of unmodified starch and high amylose starch, as explained above. The various components of the adhesive composition can be present in the adhesive composition in the amounts described above. It is particularly preferable that the maximum expansion temperature of the microspheres (Tmax) is a temperature equal to or less than the total setting temperature of the adhesive composition. If desired, additives or other components can be added to the adhesive composition to raise its setting temperature. It is desirable that the total adhesive set temperature be at least as high as the Tmax of the expandable microspheres, and particularly desirable that the total adhesive set temperature be at least 30°F (-1.1°C) higher than the Tmax of expandable microspheres.
    [0061] In the method of forming the insulating sheet, a predetermined amount of the adhesive composition is applied to the first surface of the paper backing. The adhesive composition can be applied in any desired configuration, including, for example, a series of dots, stripes, waves, checkerboard pattern, a series of polyhedra, and combinations thereof. In addition, the adhesive composition can be applied to the first surface in a series of rollers. In addition, if desired, the adhesive composition can be applied to the first side as a substantially flat sheet of adhesive, which covers all or part of the first side of the paper backing. The adhesive composition can be applied in any desired thickness, and is desirably applied in a thickness of about 0.04 inches. In embodiments where the composition is applied in the form of a cylinder, it may be desirable that the height of each cylinder is approximately the same as the diameter of each cylinder. The cylinders can be applied to the first surface in any configuration, desirably each cylinder is spaced a substantially equal distance between each cylinder. It is particularly desirable for the separation between adjacent cylinders to be about twice the height of the cylinders. The adhesive composition can be applied in the presence of heat if desired; however, it is important that the heat on application is not as high as to completely set the adhesive composition.
    [0062] After the adhesive composition has been applied to the first side of the paper liner, the paper liner with wet adhesive can be exposed to heat and/or radiation energy to begin to fix the adhesive composition. The adhesive composition therefore holds the components, including the plurality of microspheres, in place and adheres them to the surface of the paper backing. It may be desirable to only partially fix the adhesive composition, thus providing a composition that secures the components and keeps them affixed to the surface of the paper liner, but is not completely fixed. As explained above, only partial fixation of the adhesive composition (ie, leaving a greater amount of moisture in the adhesive, such as at least 10% moisture content) allows the expandable microspheres to spread.
    [0063] After fixing the adhesive, the paper backing is then exposed to heat and/or radiation energy sufficient to expand the plurality of microspheres. In one embodiment, the wet adhesive paper liner is exposed to heat at a temperature sufficient to expand at least most of the microspheres. In another embodiment, the wet adhesive paper liner is exposed to sufficient microwave or infrared energy to expand at least most of the expandable microspheres. The resulting product is a paper liner having an adhesive that has expanded microspheres on it. The adhesive composition can then be exposed to heat and/or radiation energy sufficient to completely fix the adhesive composition.
    [0064] If desired, after applying the adhesive composition to the first side of the paper liner, a second paper liner having a first side and a second side may be provided and the first side of the second paper liner applied to the surface of the composition adhesive applied, forming an intercalated configuration. Thereafter, expansion of the microspheres and fixation of the adhesive can take place as explained above.
    [0065] The present invention can be better understood by analyzing the following examples, which are not limiting and are intended only to help explain the invention. EXAMPLES Example 1 - formation of an adhesive with improved insulation properties
    [0066] An adhesive composition was prepared having the following composition:
    1 sodium tetraborate 2 sodium hydroxide, 50% FCC, Rayon 3 glycerol, glycerin, USP 99.7% 4 Proxel GXL, 1,2-benzoisothiazolin-3-one 5 Expancel® microspheres
    [0067] The water (1) was mixed with the crosslinker, and the cooked starch was added. The mixture was heated in a bath at 140°F (60°C). The alkaline agent was added to the mixture, and mixed for two minutes to form a gel. The mixture was then removed from the bath, and water (2) was added. The mixture was mixed at high speed for 5 to 10 minutes. During this mixing process, a separate mixture of water (3), humectant and unmodified starch was mixed until smooth. The two mixtures were combined and mixed until smooth. Preservatives were then added and the resulting mixture was mixed for 10 minutes. The expandable microspheres were then added and the mixture mixed for 10 minutes. Example 2 - formation of an adhesive with improved insulation properties
    [0068] An adhesive composition was prepared having the following composition:
    1 sodium tetraborate 2 glycerin or urea
    [0069] Water (1) is introduced into a first mixer and heated to 110°F (43°C). To this heated water were added the starch with high amylose content, the caustic soda globules and the primary crosslinker. In a second mixer, water (2) is introduced and heated to 98°F (37°C). Secondary crosslinker A, unmodified starch, secondary crosslinker B and wetting agents are added and mixed. The two mixers are combined and mixed. Expandable microspheres are added to the resulting mixture. Example 3 - Comparison of several stickers
    [0070] Four adhesive compositions were prepared (C1, C2, C3, and I), which are as follows: Composition C1 included an adhesive composition based on unmodified corn starch (Stein-Hall adhesive) without expandable microspheres ; Composition C2 included an adhesive composition based on unmodified cornstarch (Stein-Hall adhesive) with Dualite 130W microspheres; Composition C3 included a starch-based adhesive composition produced from a blend of unmodified corn starch and high amylose corn starch; and Composition I included a starch-based adhesive composition produced from a blend of unmodified corn starch and high amylose corn starch with Dualite 130W microspheres. The adhesives were used in forming corrugated rolls having different combinations of 18#, 23# and 33# paper for the liner and medium, and were evaluated after drying. The results are summarized below.

    * Paper cross section seen in Figure 2 ** Paper cross section seen in Figure 3 *** Paper cross section seen in Figure 4
    [0071] Total tear (FT) indicates that the peel strength of the adhesive had sufficient strength, and as such the peculiar strength cannot be measured. Examining the generated data, several observations were made. Firstly, the adhesive composition of the invention was observed to have better peculiar strength than the control adhesive and the microsphere control adhesive. Furthermore, each of the tests using composition I (inventive) was observed to have a visible thread and/or visible expansion, and thus it can be concluded that the composition of the invention forms better threads (recesses) than without microspheres. As can be seen with the C3 control composition, for example, using a composition using a high amylose adhesive without microspheres can lead to undesirable distortion of the transverse edge direction, especially for light weight paper. Additionally, it has been observed that the adhesive composition of the invention can be useful in the thinnest liner-medium without any deformation, and a high curling speed can be used. Due to the expansion of the microspheres between the middle and the lining and also in the fillet recesses, the thermal resistance of the article can be increased due to the rigidity and strength of the article, which maintains the half-lining configuration.
    [0072] As can be seen, Composition I was very successful when used at each grade of paper, and particularly successful when used at the lowest grade of liner and middle paper (Assay 12). This study was observed to operate very well at the junction, and provided smooth sheets.
    权利要求:
    Claims (20)
    [0001]
    1. Adhesive composition, characterized in that it comprises: (a) from 20 to 40%, by weight of the adhesive composition, of a starch component; (b) an alkaline component; (c) sodium tetraborate; (d) water; and (e) from 0.5 to 5%, by weight of the adhesive composition, of a plurality of expandable microspheres; wherein said starch component is selected to allow complete gelatinization of said starch component at a temperature equal to or greater than the temperature at which said expandable microspheres expand.
    [0002]
    2. Adhesive composition according to claim 1, characterized in that said starch component comprises a starch composition having an amylose content of 50% or more.
    [0003]
    3. Adhesive composition according to claim 1, characterized in that said starch component comprises: (a) an unmodified starch composition; and (b) a starch composition having an amylose content of 50% or more.
    [0004]
    4. Adhesive composition according to claim 3, characterized in that said adhesive composition comprises said unmodified starch composition in an amount of 20% by weight of said adhesive composition and said starch composition has a content of amylose of 50% or more in an amount of 4% by weight of said adhesive composition.
    [0005]
    5. Adhesive composition according to claim 1, characterized in that said alkaline component comprises sodium hydroxide.
    [0006]
    6. Adhesive composition according to claim 1, characterized in that said expandable microspheres comprise polymeric microspheres that expand in the presence of heat and/or radiation to form an insulating foam.
    [0007]
    7. Adhesive composition according to claim 6, characterized in that said expandable microspheres begin to expand at a temperature of 180°F (82°C) to 210°F (99°C).
    [0008]
    8. Adhesive composition according to claim 6, characterized in that said expandable microspheres have a maximum level of expansion at a temperature of 250°F (121°C) to 280°F (138°C).
    [0009]
    9. Adhesive composition according to claim 1, characterized in that said plurality of expandable microspheres is present in an amount of 0.5% to 5% by weight of said adhesive composition.
    [0010]
    10. Method of preparing a corrugated product, characterized in that it comprises the steps of: (a) providing a first paper liner that is planar and has a first side and a second side; (b) providing a second paper liner having a plurality of flutes each having a ridge and a depression; (c) preparing an adhesive composition as defined in any one of claims 1 to 9, comprising the steps of: (i) combining a starch component having an amylose content of 50% or more, an alkaline component, a crosslinker, and water to form a starch mixture; (ii) cooking said high amylose starch mixture to form a cooked starch mixture; (iii) adding the unmodified starch component to said cooked starch mixture; and (iv) adding a plurality of expandable microspheres to said cooked starch mixture; (d) applying said adhesive composition to the ridges of each of said flutes; (e) matching the ridges of said ridges with a surface of said first side of said planar paper liner to form a composite structure in which the first paper liner and second paper liner contact each other at said ridges of said stretch marks; and (f) curing said adhesive composition in said composite structure by heating to a first temperature and a second temperature, wherein said first temperature and said second temperature differ by from 20°F to 40°F.
    [0011]
    11. The method of claim 10, characterized in that said step of placing said ends of said flutes on said first side of said flat paper liner comprises using pressure to secure said ends of said first side .
    [0012]
    12. The method of claim 10, characterized in that said first temperature is from 138°F (59°C) to 156°F (69°C).
    [0013]
    13. Method according to claim 10, characterized in that said second temperature is from 180°F (82°C) to 210°F (99°C).
    [0014]
    14. Method of manufacturing an insulating sheet, characterized in that it comprises the steps of: (a) providing a planar paper sheet having a first side and a second side, said first side having a surface with sufficient structure to accommodate an insulating component; (b) preparing an adhesive composition as defined in any one of claims 1 to 9, comprising the steps of: (i) combining a high amylose starch component, an alkaline component, a crosslinker, and water to form a starch mixture; (ii) cooking said starch mixture having an amylose content of 50% or more to form a cooked starch mixture; (iii) adding the unmodified starch component to said cooked starch mixture; and (iv) adding a plurality of expandable microspheres to said cooked starch mixture; (c) applying said adhesive composition to said surface of said first side of said sheet of planar paper to form a sheet with an adhesive composition applied; (d) heating said sheet with said applied adhesive composition to a first temperature sufficient to expand said expandable microspheres; and (e) heating said sheet with said applied adhesive composition to a second temperature sufficient to fully cure said adhesive composition.
    [0015]
    15. The method of claim 14, characterized in that said starch component is selected to allow complete gelatinization of said starch component at a temperature equal to or greater than the temperature at which said expandable microspheres expand .
    [0016]
    16. Method according to claim 14, characterized in that said starch component comprises a mixture of unmodified starch and starch that has an amylose content of 50% or more.
    [0017]
    17. Method according to claim 14, characterized in that said step of applying said adhesive composition to said first side of said flat sheet of paper comprises applying said adhesive composition in such a way that said plurality of microspheres Expandables is applied in a selected configuration from the group consisting of dots, stripes, waves, checkerboard patterns, any general polyhedron shapes that have flat bases, cylinders, and their combinations.
    [0018]
    18. Method according to claim 14, characterized in that said first temperature is insufficient to fully cure said adhesive composition.
    [0019]
    19. The method of claim 14, characterized in that said first temperature is from 180°F (82°C) to 210°F (99°C).
    [0020]
    20. The method of claim 14, characterized in that said second temperature is 20°F to 40°F greater than the Texp of said expandable microspheres.
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    同族专利:
    公开号 | 公开日
    KR20130106397A|2013-09-27|
    BR112013004955A2|2016-08-16|
    US20130160945A1|2013-06-27|
    US9580629B2|2017-02-28|
    CN103189460B|2014-10-29|
    MX350366B|2017-09-05|
    US20140238586A1|2014-08-28|
    PL2614124T3|2018-10-31|
    JP5639272B2|2014-12-10|
    WO2012033998A2|2012-03-15|
    US20190218720A1|2019-07-18|
    JP2013537249A|2013-09-30|
    KR101420581B1|2014-07-16|
    EP2614124A4|2015-02-11|
    EP2614124B1|2018-04-25|
    CN104669757A|2015-06-03|
    US20170130399A1|2017-05-11|
    US10208429B2|2019-02-19|
    US20190136456A1|2019-05-09|
    CN104669757B|2018-01-09|
    EP2614124A2|2013-07-17|
    WO2012033998A3|2012-07-05|
    CN103189460A|2013-07-03|
    MX369481B|2019-11-11|
    MX2013002701A|2013-06-05|
    US8747603B2|2014-06-10|
    MX2019010073A|2019-11-21|
    ES2677972T3|2018-08-07|
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    法律状态:
    2018-02-06| B25A| Requested transfer of rights approved|Owner name: HENKEL US IP LLC (US) |
    2018-02-27| B25A| Requested transfer of rights approved|Owner name: HENKEL IP AND HOLDING GMBH (DE) |
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: D21H 19/54 (2006.01), B31F 1/20 (2006.01), B31F 1/ |
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-04-07| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-10-06| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US38164210P| true| 2010-09-10|2010-09-10|
    US61/381,642|2010-09-10|
    PCT/US2011/050965|WO2012033998A2|2010-09-10|2011-09-09|Improved adhesive having insulative properties|
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