MXPA98005214A - Corrugated adhesive to the insta - Google Patents

Abstract

An instant corrugated adhesive composition comprising a dry blend of starch and a dried pre-solubilized cellulosic extract. The composition can be easily rehydrated with water to produce a corrugated adhesive. Corrugated Eladhesive is formulated without boron compounds and with minimal or no addition of alkali. The dried pre-solubilized cellulose extract, which includes hemicellulose as a main component, functions as the carrier portion of the corrugated adhesive. No initial cooking step is required to produce the carrier and rehydration can be carried out at ambient temperatures.

Description

"ADHESIVE CORRUGATED INSTANTLY" BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to corrugated adhesive compositions based on starch. In particular, the invention relates to a dry mix composition that can be easily rehydrated with water to make a corrugated adhesive. The adhesive is made with boron compounds and with a minimum amount of alkali or without added alkali.

THE RELATED TECHNIQUE There is an ever increasing pressure on the part of the customer to reduce or eliminate the chemicals normally used to corrugate the adhesive formulations. This market trend is being driven by environmental discharge and safety concerns. There is also a need to corrugate adhesives that are easy to use and that are stable over extended periods of time. Commercially acceptable corrugated adhesives having these characteristics have not been described so far.

In the corrugation process, the adhesive is commonly applied to the corrugation groove tips. Then, a flat, uncorrugated paper liner is applied against the coated strips of the adhesive as they pass between a corrugation roller and a pressure roller. The resulting product has the corrugated medium on one side and a flat liner on the other side and is called a one-sided portion. The single-sided portion is used "such and such" (called "single-sided" cardboard) or an adhesive may be applied to the streaked tips of the single-sided portion and a second flat sheet may be applied in the same way as the first in what is called a "double-sided" or "double-back" operation. The second liner sheet is treated with heat and reduced pressure (relative to the pressure used to produce a single-sided portion) immediately after contact with the adhesive. Starch-based adhesives that can be of the carrier, non-carrier, and carrier-non-carrier type are commonly used in corrugated board manufacturing processes. In carrier-type adhesives, a portion of the starch (or dextrin) forms a carrier, often known, as the gelatinized phase, which suspends the rest of the starch which is in a non-gelatinized state. Under conditions of heat and pressure, the ungelatinized starch hydrates and rapidly gelatinizes to hastily increase the viscosity and adhesiveness of the adhesive composition. In non-carrier type additives, all starch is lightly cooked or swelled with heat and caustic soda for viscosity. Finally, carrier-non-carrier type adhesives have a portion of the starch which forms a carrier and which is responsible for about half the viscosity and the remaining viscosity is obtained by slightly swelling the uncooked starch. A water soluble adhesive composition is described in U.S. Patent No. 2,716,613. The adhesive consists of a lignocellulose that hydrolyzes under high temperature and pressure in the presence of moisture. A water-soluble reaction product is recovered and concentrated to dryness. The rehydration is achieved by forming a slurry with methanol and reflux while passing ammonia through it. This composition can also be filtered and dried. A heraicellulose additive for paper coating compositions is described in U.S. Patent No. 2,772,981. Hemicellulose is described as a composition that can completely replace the adhesive component in paper coatings, but is preferably added with starch, - dextrin or a similar material. The patent does not disclose a dry rehydratable composition. Corrugated adhesives having a solubilized fiber component are described by Fitt in U.S. Patent Number 5,358,559 and by Giesfeldt et al., "In U.S. Patent Number 5,503,668. employing the in situ solubilization processes In contrast to the present invention, the aforementioned references do not disclose dry rehydratable adhesive compositions having commercially acceptable characteristics for use in the corrugating industry In the present specification and claims, all the parts and percentages are in weight / weight (w / w) unless otherwise specified.

COMPENDIUM OF THE INVENTION A dry-mix composition of the extracted hemicellulose material, defined herein as a dry-free-flowing alkali-extracted plant fiber having from about 25 percent to about 100 percent and preferably from about 70 percent to 100 percent a hundred of soluble base material in dry, and starch, can be rehydrated by adding water without any other ingredients to produce a corrugated adhesive. The amount of the hemicellulose material extracted in the dry mix composition is generally from about 5 percent to about 50 percent and preferably from about 8 percent to about 30 percent. The extracted hemicellulose material functions as the carrier portion of the adhesive. Cereal grains are a source of important hemicellulose and in a preferred embodiment, the extracted hemicellulose material is extracted from corn fiber or wheat fiber, with corn fiber being preferred. The variability in the percentage of the soluble materials in the extracted hemicellulose material (which will sometimes be referred to herein as "the extract" or "extracts") will affect the amount required to produce the dry blend composition, with the highest percentages of soluble materials allowing the use of smaller amounts of the extract. For example, an extract that has 100 percent soluble materials can be used at lower concentrations than the extract that has 50 percent soluble materials. If we assume that the extract consists of 100 percent soluble materials, then the percentage of soluble materials available from the extract in the composition of - Dry mix should be from about 8 percent to about 15 percent and preferably from about 9 percent to about 14 percent, based on the total weight of the dry mix composition. The corrugated pasta of the invention is prepared without a cooking step by hydrating the dry mix composition in a single tank, high or low shear apparatus, intermittent mixer or continuous mixers such as the screw single screw extrusion apparatus. Twins Warner & Pfleide the rotary feed mixer, Baker Perkins Rotofeed or a static mixer from Kenis Corporation. Hydration is achieved by mixing from about 5 to 10 minutes or for a period of time sufficient to hydrate the composition in a uniform paste. Correspondingly, a corrugated adhesive is obtained instantly without adding boron compounds and with minimal addition or no addition of alkali. In most applications, the need to add alkali is avoided when a sufficient amount of alkali is present in the extract to provide a pH of about 7 to about 14 in the adhesive paste. Because the carrier paste is pre-solubilized with alkali, sufficient alkali will usually be present to achieve the required pH to form a good bond ("caustic" grip on the paper) and decrease the gel temperature.

DESCRIPTION OF THE PREFERRED MODALITIES The dry mix composition comprises an extracted hemicellulose material and starch. The composition is produced without boron compounds (e.g., no borax and no boric acid) and, depending on the type of starch employed, can be produced without added alkali or a minimum amount of added alkali. The amount of the hemicellulose material extracted in the dry mix composition is generally from about 5 percent to about 50 percent and preferably from about 8 percent to about 30 percent. These scales, however, propose using extracts having from about 25 percent to about 100 percent, preferably from about 70 percent to about 100 percent, of a soluble base material in dry form and, as mentioned above, the variability in the percentage of the soluble materials in the extract will affect the amount required to produce the dry blend composition, as will be apparent to those skilled in the art based on the present exposure. Extracts that have higher percentages of soluble materials can be used in smaller amounts than extracts that have smaller percentages of soluble materials. The percentage of soluble materials available from the extract in the dry mix composition should be from about 5 percent to about 50 percent and preferably from about 8 percent to about 30 percent based on the total weight of the blend composition dry. The extracted hemicellulose material referred to herein as a dried pre-solubilized cellulosic extract has from about 3 percent to about 10 percent moisture and functions as the carrier or cooked portion when the adhesive is hydrated. The corrugated dough of the invention is prepared by hydrating the dry mix composition in a single tank or a continuous mixer without a primary cooking step to produce the carrier portion. Hydration is achieved by mixing the dry mix composition with sufficient water to produce the adhesive paste having a total moisture content of about 65 percent to about 80 percent. Mixing is continued for approximately 5 to 10 minutes or for a sufficient time (which may be shorter or longer - prolonged) to hydrate the composition in a uniform paste. The hydration temperature is relatively low, usually from about 18 ° to 52 ° C and the time required for hydration is usually shorter at higher temperatures. Accordingly, a corrugated adhesive is obtained instantly with minimal addition or no addition of alkali and there is no need for boron compounds in the formulation. When the starch is a corn starch, such as pearl starch, the need to add alkali is avoided when sufficient residual alkali is present in the cellulosic extract to provide a pH of about 7 to about 14 in the adhesive paste. If alkali is needed, however, it can be added before or after the dry mix composition is added to the water. This is related to the gelatinization temperature that can vary depending on the type of starch used. For example, we have found that appropriate corrugated additives can be produced by not using added caustic when barley starch is used. Accordingly, if the gelatinization temperature of the starch is within the range of about 60 ° C to 66 ° C, the adhesive can be produced without added caustic or caustic added in a relatively small amount. Another way of looking at this is to say, that caustic is used - sufficient to bring the gelatinization temperature of the adhesive within the range from about 54 ° C to about 72 ° C, preferably from about 60 ° C to about 68 ° C, regardless of the pH value. The starch ingredient of the invention can be derived by conventional means from the root, stem or fruit of a number of plants and can have a moisture content of about 5 percent to about 15 percent, more commonly about 8 percent. one hundred to about 12 percent. Preferred starches are those produced from corn and barley but other starches such as those derived from wheat, tapioca, potato and the like are suitable. Mixtures of starches from various sources or provenances can also be used. The starches may also be modified and may be combinations of modified and unmodified starch. The dextrins may also be used by themselves or in combination with unmodified and / or modified starches. Low gelatinization temperatures are preferred and barley is an unmodified starch due to this reason. Corn starch, however, having a relatively high gelling temperature is preferred when economy is the most important consideration.

The extracted hemicellulose material of the invention is prepared by treating the fiber of the plant with an alkaline extraction agent. Any strong base can be used, but the preferred bases are alkali metal hydroxides, more preferably calcium hydroxide, potassium hydroxide or sodium hydroxide and these are generally referred to herein as alkali. Any plant fiber that is rich in hemicellulose can be used. The preferred sources or provenances are corn fiber, including husks, ears and germ, wheat fiber and barley fiber. The most important characteristic that must be considered to select appropriate plant materials is the percentage of soluble materials, and the soluble materials do not have to be 100 percent hemicellulose. The presence of small amounts of soluble protein, other soluble celluloses, certain starches and the like is not harmful as long as they do not exceed about 50 percent, preferably about 30 percent or less and more preferably 5 percent or less of soluble materials in total. When there are too many insoluble materials, they act as a diluent and the bond strength is reduced. Insoluble materials, therefore, should not exceed approximately 75 percent of the plant material and preferably should not exceed approximately 30 percent of the plant material. Hemicellulose is a natural polymer present in many living plants and can be derived from various sources to be used in accordance with the invention. Its name derives from its close association with cellulose in the plant tissue and was once believed to be a precursor to cellulose synthesis. It is a relatively strong material that resists disintegration through mechanical shear and subsequent loss of viscosity. It is completely compatible with starch. The hemicellulose can be partially hydrolyzed if desired to reduce its molecular weight and improve its viscosity characteristics. Hemicellulose is based on a 5-membered xylan structure (pentosans) that have additional side chains such as arabano-xylan and glucuronic acid. The skeletal configuration is beta, 1, 4 links similar to those found in cellulose. Even though its molecular structure is different from starch and cellulose, the key to its similarity is the many functional hydroxyl groups available for binding. The structure for hemicellulose can vary considerably, but a generalized form of the structure will be illustrated below: The pericarp or husk of a corn kernel is a particularly good source of hemicellulose due to its high content of hemicellulose, heraicellulose can be easily extracted from it and is abundantly available. One of the largest, potential, hemicellulose sources or provenances, not contaminating (ie, not damaging to the corrugation process) is the corn fiber produced by the mai wet milling industry. A preferred type of maize fiber is dietary maize fiber sold under the designation P? RLESS® corn fiber through the Corn Products Unit of CPC International Inc., PO Box 8000, Englewood Cliffs, New Jersey 07632 USA A preferred embodiment of the invention is a dry mix composition that can be hydrated with water to produce a corrugated adhesive (which will also be referred to herein as an adhesive paste) comprising; consisting essentially of or consisting - from about 95 percent to about 50 percent starch, from about 5 percent to about 50 percent of a dried pre-solubilized cellulosic extract that contains from about 25 percent to 100 percent of a soluble material on a base in dry and no boron compound. The dried pre-solubilized cellulosic extract will contain some residual alkali and when a sufficient amount of residual alkali is present to provide a pH of about 7 to about 14 in the adhesive paste or a gelatinization temperature (which is also referenced in US Pat. present as "gel") of the adhesive of about 54 ° C to 72 ° C, preferably about 60 ° C to 68 ° C, it is not necessary to add alkali when the paste is produced. The starch will usually have a moisture content of about 8 percent to about 12 percent and the dried pre-solubilized cellulosic extract will have a moisture content of about 3 percent to about 10 percent. When the above-mentioned preferred dry blend composition is rehydrated to produce an adhesive paste, a sufficient amount of water is mixed with the mixture in. dry to bring the total moisture content up to about 65 percent ~ to about 80 percent. In a particularly preferred embodiment, a byproduct of the process described in US Patent Application Serial No. 08 / 244,036, filed on February 10, 1995, is used, the disclosure of which is hereby incorporated by reference herein in its entirety. This by-product, designated as Z-SOL and obtainable from CPC International Inc., of Englewood Clifís, NJ 07632 EUA, can be prepared as follows: 1. Dry-ground purified maize fiber is suspended in a 10-fold solution. percent in weight / volume ("w / v"). The maize fiber or purified bran can be a dietary fiber in a total of 9Q percent ("TDF") of a Vetter press cake derived from corn husks and dry milled fiber at 90 percent TDF. 2. Potassium hydroxide (KOH) is added to the purified corn fiber suspended at a concentration of 1.5 percent weight / volume and maintained at a temperature of 80 ° C for 2.5 hours in order to extract the hemicellulose (and any starch and some remaining protein) of the insoluble material, mainly insoluble cellulose, in the corn fiber. - 3. The solution of water, fiber and KOH is diluted with an equal volume of water at 80 ° C and filtered. It can be used as the rectilinear gauze filter medium. 4. The filtered material contains the soluble Z-SOL and this can be neutralized with hydrocic acid (HCl) if neutralization is desired. The Z-SOL is then precipitated using alcohol. This material can be dried by spraying or drying in an oven. 5. The dried material is milled to the correct particle size and according to the present invention then dry blended with starch to produce the dry blend composition of the present invention. The preparation of the corrugated paste of the dry mix composition is quite simple. The main concern is the time needed to hydrate the material. Initial lumps may form, and may require a few minutes before they disappear. As explained above, raising the temperature to something above room temperature will facilitate rehydration of the dry mix composition. In addition to the especially preferred embodiment for the dry pre-solubilized cellulosic extract of the invention, various other preferred embodiments which do not have the same level of purity as the Z-SOL, can be employed in accordance with the invention. The low total dietary fiber ("TDF") filter cake Vetter and the alkali-treated depleted germ can be treated in a one-step process to produce a pre-solubilized dry material containing from about 25 percent to 50 percent. 100 percent soluble materials, including hemicellulose and some soluble starch and soluble protein. In our experimental work, the alkali-treated Vetter press fiber was used in the dry mix composition at a level of 20 percent to 35 percent, while the spent alkali-treated germ was used in a mixed composition. dry at the level of 18 percent to 28 percent. In contrast, Z-SOL, which contains approximately 100 percent soluble materials, can preferably be employed within the range of 8 percent to 12 percent. This work defined a preferred concentration scale for corn fiber pre-solubilized in dry and approximately 8 percent to 30 percent. Any amount less than 8 percent does not provide a sufficient amount of the carrier to provide viscosity stability or to prevent the paste from separating after a short period of time. Any greater than approximately 30 percent of the presolubilized fiber - in dry of low content of soluble materials causes that the insoluble material deteriorates the quality of the bond. It is a theory of the invention that there may be a component in the insoluble material that is beneficial to produce a good strong bond. Possibly, the remaining cellulose with a certain amount of hemicellulose still fixed exists as small "sticky" cubes or platelets that span the spaces in the paper.

EXAMPLES EXAMPLE 1 A commercially available dry blend composition of 88 percent (C.B.) of pearl starch and 12 percent of Z-SOL was prepared in the laboratory as follows: Rehydration Add water to a 4 liter tank 2022 milliliters (water temperature is room temperature) Add a dry mix composition 675 grams Mix 10 minutes - Add alkali (50% NaOH) 31 grams Mix / Heat 10 minutes / 38 ° C Analysis Final Temperature 38 ° C Viscosity Stein-Hall: 40 seconds Gel Temperature: 62 ° C-66 ° C% Solids: C.B. 25% Stability The finished paste was placed in a water bath at 38 ° C immediately with stirring cycles using a paddle stirrer for 5 minutes in operation and 25 minutes without operation during every 30 minutes.

Time Viscosity Comments Stein Hall, sec. 1 hour 40 There was no sedimentation at the bottom of the starch, accumulation of foam in the center of the retention beaker - 2 hours 41 There was no sedimentation of starch in the bottom, the accumulation of foam in the center of the retention beaker. during 40 There was no sedimentation of the night starch in the background, nor (18 hours) foam accumulation.

EXAMPLE 2 Pilot plant trials were carried out at the Paper Science and Technology Institute (IPST) in Atlanta, GA using its 35.56 cm Langston single-sided corrugator with the C-flut rollers. The machine was operated at commercial speeds using a 19.07 kilogram Kraft liner, or a high performance liner of 15.89 kilograms both together with a medium of 11.80 kilograms. A dry blend composition of 88 percent pearl starch C.B. and 12 percent Z-SOL was prepared by adding the ingredients to a twin-hulled dry mixer and mixing 18.16 kilograms at 25 revolutions per minute for 10 minutes. The dry mix composition was rehydrated to produce a paste.

- - The corrugator applied the paste to the stria tips of the striated medium and heated just before the medium came into contact with the heated liner under pressure, forming the first bond in the process of producing a finished sheet of corrugated cardboard. The pulp was made using a 151.40 liter capacity mixer equipped with a constant speed paddle stirrer producing approximately 37.85 liters of pulp. The finished paste was transferred to an insulated storage tank with a capacity of 75.70 liters. A small blade pump circulated the paste from the storage tank to a corrugating machine on one side. The formulations and results are summarized in Table 1. The compositions have 12 percent (by weight / total weight C.B.) of Z-SOL in the carrier phase, which has characteristics similar to a completely normal starch paste formula. The 8 percent Z-SOL paste also worked reasonably well, but the paste hastily developed a layer of liquid after settling for a few minutes without agitation because it speaks an insufficient amount of solids in the carrier phase. Laboratory work with Z-SOL at 15 percent resulted in a paste finished with high viscosity. At this level of Z-SOL, the viscosity of the finished pulp increased to an unusable level. Therefore, the Z-SOL level should be less than about 15 percent. The Q4 paste (Table 1) was a compound without boron, and without alkali paste. This paste was produced with a premix of Z-SOL in a formula of total solids at 33 percent C.B. The total solids percentage C.B. of this formula is raised according to the known standards. In most commercial corrugated pastes they are within the range of 20 percent to 30 percent total solids C.B. Thirty-three percent solids C.B. Normally there would be more solids than a commercially produced carrier starch (modified or unmodified) can suspend. This higher percentage of C.B. it can be achieved with the elaborated carrier phase of the pre-solubilized plant fiber. The high percentage of solids C.B. It is important because less heat is needed by the corrugator due to the smaller amount of water that has evaporated. Since less heat is needed to evaporate water, there is more heat available to gelatinize the starch, which allows the use of pulp made with a higher gelatinization temperature than normal. In this case, a paste made with corn starch / pre-solubilized plant fiber, but without added alkali, had a gelatinization temperature within the range of 68 ° C to 70 ° C. This is compared to a gelatinization temperature of 71 ° C to 74 ° C for corn starch alone and indicates that the carrier of the pre-solubilized cellulosic extract of the invention causes a decrease in the gelling temperature. Accordingly, one embodiment of this invention is a dry composition for producing a carrier comprising, consisting essentially of or consisting of the dried pre-solubilized cellulosic extract described herein. The dry composition is rehydrated and becomes a carrier when the adhesive paste is produced in accordance with the foregoing description. The Q4 paste worked well on the 35.56-centimeter Langston IPST single-sided machine using a high-performance liner of 15.89 kilograms and a medium of 11.80 kilograms (Table 2). The paste did not show a liquid layer after settling. The last paste in Table 1, TI was made from a dry blend of Z-SOL / barley starch. This paste without added borax or caustic worked exceptionally well on the machine. The paste was hydrated very hastily and operated on the machine within 15 minutes after mixing the dry mix with the water. The gelatinization temperature was 66 ° C.

- When the barley starch was replaced by pearl starch, the gelitinization temperature decreased from about 74 ° C to about 66 ° C, making it possible to prepare a non-caustic adhesive at a normal solids level because the gelatinization temperature for the starch of barley is about 5o to 15 ° C lower than for corn starch. Other starches and modified starches that have gelitinization temperatures similar to those to barley would expect it to work in a similar way.

Table 1 Tests on the Pilot Plant Corrugated adhesive without borax, low content or no content of causutico Pastas de Álcali Pastas without Alcali Test Ql Q2 Q3 Q4 TI Date 7 Feb 23 Ab 23 Ab 24 Ab 28 Jun Type of Fiber Z-SOL Z-SOL Z-SOL Z-SOL Z-SOL Type of a bead pearl maize corn maize corn barley Substitution of soluble fiber,% 12 12 12 12 - Boron compounds No No No No No Alkali Yes Yes Yes No No Formula Agu, L 38 36 36 38 40 Heat, ° C 41 49 38 41 49 Fiber solube / pearl starch, kilograms 12.71 9.99 15. .44 18.61 13.5 Mixture, Min 10 10 10 10 10 Sodium hydroxide (50/50), grams 576 464 370 Mixture, Min 10 10 10 Finish, ° C 28.5 27.5 34 36.5 3 £ Finishing Viscosity, Seg (Stein Hall) 47 67 26 67 26 Finishing gel temperature, ° C 61 63 64.5 68-70 66 Table 2 shows the corrugation results of the pilot plant associated with each batch of pulp. The tests were marked by: pre-mix code number, high performance liner test with - low paper temperature ("HPL") or high performance liner with high paper temperature ("HPH"), and a rubber roll space in thousandth of 2.54 centimeters: Tests of Ql Ql-HPL-8 Ql-HPH-8 Ql-HPL-12 Ql-HPH-12 Ql-HPL-20 Ql-HPH-20 Tests of Q2 Q2-HPL-12 Q2-HPL-20 Tests of Q3 Q3-HPL-12 Q3-HPL-20 Tests of Q4 Q4-HPL-8 Q4-HPL-12 The samples of each test were taken at 91.44 meters per minute, 152.40 meters per minute and 213.36 meters per minute (or a higher speed before full delamination). Shore crushing, flat crushing, single-sided dry pin adhesion and fiber pull percentage were measured for each sample - using -the TAPPI test methods - * -. All numbers are good or better than the results on this machine for conventional carrier starch adhesives. The results of shore crushing Ql were superior to all shore crushing results of previous tests. The untreated bond measurement was made by inserting a device with two wedges placed across each other on the edges of the single-sided liner board, at a distance of 15.24 centimeters from the point of suppression on the discharge side of the cartridges. Corrugated rollers. The wedges clear the lining, while producing an upward force on the outer edges of the medium causing it to begin to delaminate from the lining board. The delamination progresses inward to the center as the velocity of the - ^ Technical Association of Pulp and Paper Industry, Inc. (TAPPI) tests included Dry Pin Adhesion (TAPPI T821) for bond strength, bank crush and flat crush. Details of the methods are available in TAPPI Test Methods 1989, available from TAPPI, One Dunwoody Park, Atlanta, GA 30341 E.U.A. - machine. An intense untreated bond produces little delamination beyond the outer edge of the medium. As the speed of the machine increases, the untreated bonding is weakened and the delamination of the medium from the liner advances inward to the center of the continuous one-sided tape. The measurements used to represent the untreated binding strength are taken from Batelka, J.J., Tappi J. 75 (10): 94 (1992) The Institute of Paper Science & Technology, Atlanta, GA. This work used only induction time. This is the time required to form a sufficient amount of untreated bond to retain at least a certain amount of the medium in the center of the liner. For example, a typical induction time was 80 milliseconds. In other words, it took at least 80 milliseconds from the time the paper exited the fastening point so that the untreated bond solidified enough to retain a certain amount of the lining medium as the medium went beyond the surface. cradle. The induction time was calculated using formula (1). (1) Time (ms) = [15.24 centimeters / machine speed x 12] x 60 x 1000 The induction time of the pearl carrier starch paste was 50 milliseconds (ms). Our pastas - Carrier starch were between 60 and 80 milliseconds. The minimum induction time is the minimum time necessary for a bond to form.

Picture ADHESIVE CORRUGATED INSTANTLY WITHOUT BORAX RESULTS OF THE PIGOT PLANT OF LIGAZON WITHOUT TREAT IPST (2) Pasta - Speed Max Induction Time IPST Test No. (meters / minute) Minimum, miUseconds Ql-HPL-20 108.20 Q2-HPL-12 133.50 68 Q2-HPS-20 126.49 72 Q3-HPH-12 118.26 77 Q3-HPH-20 110.64 83 Q4-HPL-12 105.16 87 Q4-HPL-8 118.26 77 (2) Langston IPST 35.56-centimeter single face machine with wedge inserted at a distance of 15.24 centimeters from the point of attachment.

Table 2 Test Results One-Sided IPST CPC February Test Crushing Single-Sided Crushing Shore Pulling Fiber Plane (2.54 cm / (Kgs / cm2) Adhesion (%) To Pin In (2.54 cm / 24 In To Inward ID Prom Prom Dev Dev Dev Dev Sample Normal Normal Normal meters per minute 207-Q1-HPL-8 91.44 23.2 2.0 2.52 .070 72.5 7.9 Average 152.40 24.4 1.0 2.67 .126 77.2 7.9 Average 213.36 24.6 2.2 2.71 .035 56.6 8.0 0% 207-Q1-HPL-12 91.44 27.0 1.9 2.64 .134 85.0 6.3 Medium 152.40 27.0 1.8 2.76 .049 90.1 2.3 Medium 213.36 25.5 3.2 2.62 .134 70.3 10.9 0% 207-Q1-HPL-20 91.44 28.4 1.3 2.61 .070 111.8 4.2 Average 152.40 28.7 1.2 2.73 .063 108.3 3.1 Average 213.36 25.5 1.5 2.76 .126 52.8 11.6 0% - - 206-P3-HPL-12 91.44 24.3 1.5 2.54 .098 73.8 11.6 Media 152. 40 25.8 1.5 2.73 .056 80.8 7.4 Medium 213. 36 23.9 1.3 3.02 .070 73.2 9.0 Media 206-P3-HPL-20 91.44 26.9 1.5 2.72 .035 96.0 11.6 Media 152. 40 27.0 2.0 2.64 .056 91.0 5.2 Media 213. 36 26.1 1.0 2.90 .070 81.2 5.6 Average 206-P3-KRH-12 91.44 22.5 1.7 2.17 .077 102.8 3.7 Average 152.40 24.3 2.3 2.14 .098 82.6 4.1 Average 213. 36 24.1 1.8 2.26 .063 73.7 5.8 Average 206-P3-KRH-20 91.44 26.3 2.1 2.33 .079 112.7 5.9 Average 152. 40 24.1 1.6 2.13 .079 103.9 4.9 Medium 213.36 22.2 2.0 2.33 .084 93.6 6.4 Medium 207-Q1-HPH-8 91.44 23.8 1.9 2.60 .056 68.3 3.7 Average 152. 40 25.4 1.7 2.71 .063 70.9 2.9 Average 213. 36 22.8 2.8 2.62 .098 58.5 5.3 Average 207-Q1-HPH-12 91.44 24.8 1.9 2.54.119 79.1 5.4 Media 152. 40 25.6 1.0 2.70 .098 91.5 5.9 Average 213. 36 24.0 1.0 2.67 .119 61.2 8.1 Average 207-Q1-HPH-20 91.44 28.1 1.7 2..64 .119 107.5 6.3 Average 152.40 24.7 1.5 2. 81 .070 109.2 6.5 Average 182.88 26.3 1.5 2 .80 .079 105.5 4.8 Average 213.36 24.4 2.7 2. 82 .119 99.0 5.9 Average Test Results One-sided CPC Test Crushing Crushing Single Face Shore Traction Fiber Plane (2.54 c / (Kgs / cm2) Adhesion of (%) To Pin In (2.54 cm / 24 In Inward Identification of Prom Dev Prom Dev Def Dev Dev Sample Normal Normal Normal meters per minute 423Q2HPL-12 91. .44 21.2 2.1 2.21 .035 77.7 5.9 M 152. 40 19.9 1.2 2.21 .126 81.3 4.7 M 213. 36 21.0 1.3 2.31.105 75.3 1.7 M 423Q2HPL-20 91.44 19.7 1.3 2.14 .042 107.6 4.7 M 152.40 20.3 1.5 2.27 .084 97.9 3.7 M 213.36 21.1 2.2 2.21 .084 68.4 2.4 M - - 423Q3HPL-12 91.44 20.1 1.9 2.21 .063 111.4 3.9 M 152.40 20.3 1.9 2.21 .112 90.8 6.8 M 213.36 21.8 1.8 2.31 .183 52.7 9.3 OR 423Q3HPL-20 91.44 22.8 2.2 2.12 .035 114.0 6.1 M 152.40 20.5 2.2 2.21 .042 51.2 7.8 O 187.45 22.3 1.3 2.17 .070 44.5 9.2 OW 423Q4HPL-12 182.88 19.7 1.9 2.47 .091 57.2 13.1 or 423Q4HPL-08 91.44 19.9 2.0 2.33 .126 89.2 2.5 M 152.40 21.3 1.4 2.47 .056 87.5 1.9 M 182.88 21.2 1.4 2.36 .056 67.1 9.7 M 213.36 19.7 1.4 2.83 .084 56.1 8.6 0 424Q4HPL-12 91.44 22.1 2.2 2.29 .105 101.4 2.5 M 152. 40 20.0 2.7 2.27 .084 88.2 5.1 M 4244Q4HSKR-08 91 .44 24.0 1.5 2 .10 .042 81.0 8.3 M 152. .40 21.9 0.9 2., 23 .042 84.0 5.2 M 182. , 88 22.4 2.2 2., 31 .035 81.4 3.5 M 198 .12 25.0 1.8 2 .09 .091 63.8 7.8 M 424Q4HSKRH-12 91. .44 25.7 1.1 2. .12 .070 108.6 2.4 M 152. .40 24.7 1.3 2., 18 .042 104.9 5.3 M 167. , 12 22.1 1.5 2., 15 .028 86.3 7.5 M 182 .88 24.4 2.0 2 .15 .077 68.1 27.1 0 Table 2A Test Results Single-sided CPC test Crushing Crushing Single-sided Shore pull Fiber plane (2.54 cm / (Kgs / cm2) Adhesion of ( %) To Pin Inside (2.54 cm / 24 L to Inward) Identification of Prom Dev Prom Dev Def Dev Dev Sample Normal Normal Normal meters per minute 628-T1-KRH-12 91. .44 23.0 1.9 2.02 .049 94.7 3.8 10 152. 40 21.3 2.1 2.13 .042 95.4 1.8 0 * 182. 88 21.6 1.5 2.11 .063 78.1 11.6 0 213. 36 22.0 1.7 2.15 .056 77.4 6.7 EXAMPLE 3 All the Q-series pastes made with Z-SOL showed good viscosity stability over 24 and 48 hours. Table 3 shows the results. The pastes were retained overnight in an unheated container. The temperature and the viscosity were measured and then the pulp was heated to 38 ° C in a water bath and the - viscosity re-measured. The viscosity of the cold paste did not increase through the viscosities of the initial finished paste. However, the viscosity of the cold paste did not show the kind of increase in viscosity through 24 and 48 hours that would be expected for a starch carrier paste. The viscosities of the reheated pulp for 24 and 48 hours were surprisingly very similar to the viscosity of the initial finished pulp. This was also not to be expected for the starch-bearing paste. Table 3 Pilot Plant Testing Adhesive corrugated instantly without boron compound, with high, low or none content - viscosity is expressed in seconds Stein-Hall Paste Viscosity Viscosity during Viscosity during Finished Ini- 24 Hrs. 48 Hrs. Comments cial / Temp. In Hot Cold In Hot Cold 38 ° C 38 ° C Ql 60 / 28.5 ° C 61/20 ° C 36 liquid layer Q2 67 / 27.5 ° C 80/22 ° C 60 88/20 ° C 50 liquid layer Q3 26 / 33.9 ° C 27/22 ° C 25 30/20 ° C 25 liquid layer Q4 67 / 36.5 110/21 ° C 66 no liquid layer Rl 60/42 ° C 500/29 ° C 500 no liquid layer YES 27/37 ° C 38/29 ° C 31 liquid layer - EXAMPLE 4 In addition, Table 4 shows how stable Q4 was. We tried to cut this pasta at the end of the test. After almost 20 minutes in a high shear mixer, the paste only lost a viscosity of 15 seconds from Stein-Hall. A much greater fall was to be expected. Table 4 Test pilot plant Pasta Q4 High shear mixer (1) Viscosity Time, Min. Stein-Hall, Sec. 0 73 1 73 3 72 5 68 7 67 9 64 13 62 19 58 (1) diameter head of 10.16 millimeters, 3 horsepower, 3500 revolutions per minute - EXAMPLE 5 The pre-solubilized cellulose extracts containing less solubilized fibers than Z-SOL were tested. A greater amount of this material has to be used compared to Z-SOL to provide a soluble material sufficient to suspend the pearl starch. Table 5 illustrates the results for the two pastas. The first formula, Rl, was elaborated with the dried pre-solubilized cellulose extract produced from the fiber of the Vetter press pre-treated with alkali. This paste was prepared with a pre-mix of 35 percent dried presolubilized cellulose extract and 65 percent corn starch. Sulfuric acid was added to the paste to neutralize a certain amount of caustic remaining in the extract after processing, but the results indicated that this was not necessary. The quality of the carton made using this material without borax and without added alkali (pH neutral) indicated that a concentration of 35 percent is the maximum amount that can be used in a corn starch composition without added caustic. The second formula, SI, used spent flake treated in the same way as the Vetter press cake. This pasta was made with a premix of 28 per - one hundred percent of the presolubilized dried cellulose extract and 72 percent of corn starch. The paste was adjusted to a neutral pH due to the same reasons that we neutralized the material of the Vetter press. The paste pasted the cartons together but the results indicated that a concentration of 28 percent was the upper limit for this material in a neutral paste (without added alkali). (Adding alkali to the paste (paste S8) improves the bonding quality but a cut in the percentage of substitution is also required because the alkali increases the viscosity of the finished paste).

TABLE 5 Pilot plant tests Soluble fiber of lower purity Process Solidair BEPEX Rl Test SI S8 Press Fiber Type Depleted flake depleted flake Vetter Type of starch pearl Maize Corn Maize Substitution of soluble fiber,% 35 28 58 Boron Compound No No No Alkali Added No No Yes Formula Water, L 43 54 33 Heating, ° C 49 49 38 Soluble fiber, kgs. 5.56 4.77 2.54 Mixture, Min 5 2 Sulfuric acid 290 220 Mixture, Min 5 5 Pearl starch 22.75 34.2 294 Mixture, Min 10 10 10 Temp. Finishing, ° C 42 37 Finish viscosity, seconds Stein-Hall 60 27 84 Temp. of finishing gel, ° C 74 77 Finish pH 5.9 - - Table 6 Single-sided test Crushing Crushing Single-sided Shore traction Fiber plane (2.54 cm / (Kgs / cm2) Adhesion of (%) To Pin In (2.54 cm / 24 In To Inward Prom Prom Prom Dive Normal Sample Normal Normal meters per minute 627-R1-KRH-12 91.44 23.4 1.5 2.07 .042 39.2 2.3 152.40 20.0 1.3 2.03 035 15.3 3.0 182.88 Loose lining 627-R1-KRH-12 152.40 18.3 1.0 2.05 .035 18.5 4.1 182.88 Loose lining 627-S1-KRH-12 91.44 21.3 1.5 1.99 049 58.1 2.8 0 152.40 19.3 1.9 1.98 070 20.1 3.7 0 176.78 20.5 1.8 2.05 028 25.5 2.6 0 1114-S8-HPH-12 91.44 22.8 0.9 2.57 089 63.9 3.6 0 152.40 22.3 1.0 2.69 070 55.6 2.4 0 213.36 Loose lining 1114-S8A-HPH-12 91.44 25.1 1.2 2.69 105 69.5 4.4 0 152.40 23.6 1.9 2.56 056 59.4 4.5 0 213.36 21.1 1.6 2.56 070 26.5 6.8 0

Claims (20)

- - R E I V I N D I C A C I O N E S:

1. A dry mix composition that can be hydrated with water to make a corrugated adhesive comprising from about 95 percent to about 50 percent starch, and from about 5 percent to about 50 percent of a dried pre-solubilized cellulose extract containing approximately 25 percent to 100 percent of the soluble material on a dry basis, optionally added alkali and no boron compound.

The composition of claim 1, wherein the pre-solubilized cellulosic extract has a particle size less than about 80 mesh from the United States.

The composition of claim 1, wherein the dried pre-solubilized cellulosic extract is derived from plant fiber or plant grain.

The composition of claim 1, wherein the dried pre-solubilized cellulosic extract is derived from corn fiber, wheat fiber or barley fiber.

The composition of claim 1, wherein the starch is selected from the group consisting of corn starch and barley starch.

6. The composition of claim 1, wherein the dried pre-solubilized cellulosic extract contains from about 70 percent to about 100 percent of the soluble material on a dry basis.

The composition of claim 1, comprising from about 8 percent to about 30 percent of the dried pre-solubilized cellulosic extract.

The composition of claim 1, wherein the dried pre-solubilized cellulosic extract has from about 3 percent to about 10 percent moisture.

9. A corrugated adhesive composition consisting of the dry blend composition of claim 1 and sufficient water to provide a total moisture content of about 80 percent to about 65 percent. The composition of claim 9, having a pH of from about 7 to about 14. The composition of claim 9, which has a gelatinization temperature of about 54 ° C to about 72 ° C. 12. A composition for producing a carrier for a corrugated adhesive based on starch and lowering the gelatinization temperature of the starch comprising a - dried pre-solubilized cellulose extract containing from about 25 percent to 100 percent of a soluble base material in dry and residual alkali. The composition of claim 12, wherein the amount of residual alkali is sufficient to provide a pH of from about 7 to about 14 in the corrugated adhesive. The composition of claim 12, wherein the amount of residual alkali is sufficient to provide a gelatinization temperature of about 54 ° C to about 72 ° C in the corrugated adhesive. 15. A method for making an instant dry-mix corrugated adhesive comprising mixing from about 95 percent to about 50 percent starch and from about 5 percent to about 50 percent of a pre-solubilized dried cellulosic extract that It contains approximately 25 percent to 100 percent soluble material on a dry basis. 16. A method for hydrating the composition of claim 1 comprising mixing the composition with sufficient water to provide a total moisture content of about 65 percent to about 80 percent and for a sufficient time to hydrate the composition in a uniform paste . 17. The method of claim 16, wherein the sufficient time is from about 5 to about 10 minutes. 18. The method of claim 16, wherein the hydration is at a temperature of about 18 ° C to 52 ° C. A method for producing a corrugated board comprising bonding a corrugated medium to at least one liner using the corrugated adhesive composition of claim 9. The corrugated board manufactured by the method of claim 19.