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    • 专利摘要:
    tissue paper sheet, tissue paper product and tissue paper base preparation method the present invention describes dry products and, in particular, dry tissue paper substrates, including a combination of conventional papermaking fibers and microalgae . the use of a cationic retention aid in dry tissue paper substrates helps to provide a tissue paper sheet retaining microalgae without being detrimental to tissue paper properties such as gauge, specific volume, air permeability, degradation and absorbent capacity. furthermore, the use of a flocculating agent can agglomerate the microalgae and make the microalgae retention easier within the tissue paper sheet.
    公开号:BR112012030321B1
    申请号:R112012030321-0
    申请日:2011-05-03
    公开日:2020-09-29
    发明作者:Thomas Gerard Shannon；Bo Shi；Ellen Elizabeth Pelky；Jeffrey Robert Besaw；David Wesley Bernd
    申请人:Kimberly-Clark Worldwide, Inc；
    IPC主号:
    专利说明:

    This order claims the priority of the currently copying U.S. Provisional Order No. 61 / 353.74 5 entitled “ulado 5" Tissue Products Containing Microalgae Materials ", filed on June 11, 2010, on behalf of Thomas Gerard Shannon et al. (Registration No. 64655086US01). HISTORY OF THE INVENTION
    A major problem affecting the pulp and paper industry worldwide is the rising cost of suitable wood fiber. As a result, the tissue paper industry is always looking for alternative low-cost fiber species for sustainable manufacturing. Environmental groups and consumers who prefer to use green products 15 have also advocated the use of non-wood fibers as being more environmentally friendly than wood fibers. To reduce dependence on the wood pulp commodity, the use of recycled fibers may be a partial solution, but the use of recycled fibers in tissue paper products is technically limited 20 by the quality of the final product acceptable to users.
    Alternatively, certain non-wood fibers, such as fibers from arable crops or agricultural waste, are considered to be more sustainable. Examples include kenaf, flax, bamboo, cotton, jute, hemp, sisal, bagasse, corn straw, rice straw, wheat straw, hersperaloe, switchgrass. and the like. Non-wood fibers are believed to account for about 5 to 10 percent of global pulp production, but are limited for a variety of reasons, including seasonal availability, problems with chemical recovery, pulp luster, silica, etc. In addition, all terrestrial plants still contain substantial amounts of lignin. It is necessary to supply a significant amount of energy and chemicals to remove lignin to obtain fibers suitable for most papermaking.
    As another alternative, algae biomass has been proposed as an alternative source of fibers and has several advantages. In particular, algae biomass has no lignin and is known to grow faster and provide higher yields, compared to fibers collected from trees. Like trees, algae are efficient in using carbon dioxide to reduce air pollution and global warming.
    Algae is also increasingly used to reduce excess nutrients in water due to uncontrolled releases of pollutants from industry and human activities. In addition, algae cultivation does not compete with land use. Over the 10 years, different types of algae have been adapted for a variety of industrial applications. For example, adsorbent materials comprising microalgae, such as Chlorella or Spirulina, are adapted to remove toxins and odor in cigarette smoke and in the air, or use brown algae to remove heavy metals from residual water with absorbent particle sizes in the range of 500 pm ~ 2 mm. Others used Chlorella microalgae, - in combination with a consortium of prokaryotic microorganisms, to effectively purify wastewater effluents using a photobioreactor. The researchers developed methods to identify species of algae and compositions that are effective for the production of lipids, remediation of waste water and air for the production of biomass. ■
    Recent work on adapting microalgae for industrial uses has focused on refining them as biofuels, which is a result of increasingly limited fossil fuel resources and the relatively high cost of oil. Bioration, a residual material from leftover microalgae for processing biofuels, is normally used in animal feed. (See, for example, US Patent No. 6,338,866 and International Patent Publication No. WO 01/60166 to Criggall et al., Who have developed methods for making pet or animal feed using such a waste product that includes cell carcasses that remain after one or more essential fatty acids such as docosahexanoic acid (DHA) are extracted from lysed algae cells such as Crypthecodinium cohnii ;. Publication No. WO 2008/039911, for Lo et al., provides a method of optimization of palatable components for pet food that includes algae bioration).
    In many cases, the bio-processing of microalgae biomass processing is treated as waste and disposed of in landfills or compost piles. Therefore, a value-added use of microalgae biomass will be a very attractive approach. Activities in the production and use of microalgae will increase in the future because there is a demand for reducing global warming and cleaning wastewater effluents. On the other hand, the petroleum-based oil products that currently dominate the energy market are not sustainable. As a result, it is expected that a large amount of microalgae will be used for biofuel refinement processes described in U.S. Patent Application Publications Nos. 2008/0155888 for Vick et al. and 2008/0090284 for Hazlebeck et al. Bioration or microalgae leftover material for biofuel refinement processes will be abundantly available because the microalgae flour estimated as a by-product is 0.77 pounds for every pound of microalgae processed for oil. Therefore, the efficient use of such residual material for use in the manufacture of tissue paper products becomes important for any business that currently depends on oil as a raw material.
    Microalgae are usually very small. The small size creates difficulties and limits on the amount of microalgae that can be kept inside the fiber sheet, particularly in thin paper products, such as tissue paper. Small size and the lack of significant amounts of cellulosic material can also result . less resistance. Therefore, there is a demand for methods to increase the retention of microalgae from fiber sheets. Therefore, there is a need to provide a way to effectively use algae biomass in the manufacture of tissue paper products, such as facial tissue paper, toilet paper and paper towels. ABSTRACT
    In general, dry paper products e. in particular, dry tissue paper substrates, including a combination of conventional papermaking fibers and microalgae are described in this document. The use of an ionic retention aid, preferably a cationic retention aid, in the process of preparing 5 tissue paper substrates helps to provide a tissue paper sheet retaining microalgae without being detrimental to the properties of tissue paper such as such as caliber, volume, air permeability, slough and absorbent capacity. In addition, the use of a flocculating agent can agglomerate the microalgae and make the retention of the 10 microalgae easier within the tissue paper sheet. i •
    Desirably, the amount of microalgae present in the tissue paper product can be from about 1 to about 50 weight percent, more desirably from about 10 to about 40 weight percent, and even more desirably, about 15 10 to 30 weight percent based on the total weight of the fiber in the tissue paper product.
    Tissue paper products can be differentiated from other paper products in terms of their volume. The specific volume (bulk) of the tissue paper products of the present invention can be calculated as the quotient of the gauge, expressed in micrometers, divided by weight, expressed in grams per square meter. The resulting specific volume is expressed as cubic centimeters per gram. Writing paper, newsprint and other similar papers have greater strength, stiffness and density (low specific volume) compared to tissue paper products of the present invention which tend to have much larger gauges for a given weight. The specific volume of the tissue paper web can vary between about 2 to about 25 cm3 / g, more specifically between about 3 to about 30 20 cm3 / g, and even more specifically between about 4 to about 18 cm3 / g.
    The weft gauge of the tissue paper, although not important to the invention, can be at least about 90 micrometers or greater, and is desirably from about 90 to about 35 to 1,200 micrometers and particularly from about 100 to about 900 micrometers.
    The tissue paper product described here may have a specific absorbent capacity, expressed as grams of water absorbed per gram of fiber, of about 6 g / g or greater, between about 7 to about 18 g / g, or between about 8 to about 18 g / g.
    The tissue paper product described in this document may have a geometric mean tensile strength expressed in grams (strength) per 3 inches of sample width of about 26.2 g / cm (200 g / 3 ") or greater, or between about 39.4 to about 590.6 g / cm (about 300 to about 4,500 g / 3 "). Where multi-layer products are used, the tensile strength per layer should be considered equivalent to the tensile strength of the multi-layer product divided by the number of layers. BRIEF DESCRIPTION OF THE DRAWINGS
    The above aspects and other characteristics, aspects and advantages of the present invention will be better understood in relation to the following description, claims and attached drawings, in which:
    Figure 1 is a schematic flow chart of a wet-end stock, system useful for the purposes of this invention;
    Figure 2 is a schematic flowchart of a non-creped, direct-drying tissue paper manufacturing process according to this invention.
    The repeated use of reference characters in the specification and drawings is intended to represent the same or analogous characteristics or elements of the invention in different modalities. DETAILED DESCRIPTION
    It should be understood by one skilled in the art that the present discussion is only a description of the exemplary modalities, and is not intended to limit the broader aspects of the present invention, the broader aspects of which are incorporated into the exemplary construction.
    Base sheet of tissue paper, as used in this document, refers to the single layer tissue paper produced in the tissue paper machine prior to conversion to a final product. The tissue paper product, as used in this document, refers to the finished tissue paper product in which the tissue paper base sheet has been converted into a final product, such as, but not limited to, toilet paper, ■ facial tissue paper, a napkin, a paper towel or a general purpose cleaning product. The tissue paper products of the present invention can comprise one or more layers of the tissue paper base sheet. The tissue paper products of the present invention can, therefore, be single layer or multilayer. Tissue paper products can have the same mechanical properties as tissue paper base sheets, differing only in physical size or shape, such as folded or rolled. However, those skilled in the art will recognize, that tissue paper products can have different mechanical as well as physical properties, depending on the nature of the actions taken to convert the tissue paper base sheet into the tissue paper product.
    Generally, dry products and particularly dry tissue paper substrates, including a combination of conventional papermaking fibers and fibrous microalgae materials, are described in this document. Although microalgae can be incorporated into tissue paper products to make the 25 products more environmentally friendly, there are several disadvantages as a result of incorporating microalgae into tissue paper products. Such a disadvantage of using microalgae involves the poor retention of microalgae within conventional papermaking fibers due to their small sizes. Surprisingly and unexpectedly, the use of a cationic retention aid will help to reduce this retention problem and provide a tissue paper sheet containing microalgae without being detrimental to tissue paper properties such as gauge, specific volume, air permeability, sludge and capacity 35 absorbent. In addition, the use of a flocculating agent can agglomerate microalgae and make retention of microalgae easier within the tissue paper sheet. Indeed, it has been found that the specific volume and absorbent capacity increase when microalgae are incorporated into tissue paper, in particular air-dried tissue paper, which is routinely used in toilet paper and paper towels.
    Microalgae comprise a vast group of heterotrophic photosynthetic organisms, which have extraordinary potential for cultivation as energy crops. They can be grown under difficult agroclimatic conditions and are capable of producing a wide range of commercially interesting by-products such as fats, oils, sugars and functional bioactive compounds. As a group, they are of particular interest in developing future renewable energy scenarios. Certain microalgae are effective in producing hydrogen and oxygen through the biophotolysis process, while others 15 naturally produce hydrocarbons that are suitable for direct use as high-energy liquid fuels. It is this last class that is the object of this document.
    Once grown, the costs of collecting and transporting algae species are less than those of 20 conventional crops and their small size allows for a range of economical processing options. They are easily studied under laboratory conditions and can effectively incorporate stable isotopes in their biomass, thus allowing effective genetic and metabolic research to be carried out in a much shorter period of time than conventional plants.
    The microalgae for use in the methods and tissue paper product described herein can be marine or freshwater microalgae. Microalgae can be selected from, but are not limited to, non-mobile, flagellate, diatomous and blue-green algae. Microalgae can be selected from, but are not limited to, families. of Dunaliella, Chlorella, Tetraselmis, Botryococcus, Haematocoacus, Phaeodactylum, Skeletonema, Chaetoceros, Isochrysis,
    Nannochloropsis, Nannochloris, Pavlova, Nitzschia, Pleurochrysis, Chlamydomas or Synechocystis.The microalgae desirably will have a size in the longest dimension less than 500 pm and preferably less than 300 um, and even more preferably less than 200 pm.
    Desirably, the amount of microalgae present in the tissue paper product can be about 1 to 5 about 50 weight percent, more desirably about 10 to about 40 weight percent, and even more desirably, about 10 to 30 weight percent based on the total weight of the fiber in the tissue paper product. ’
    Unexpectedly, the inclusion of microalgae in the tissue paper substrate results in an increase in specific volume and water retention. This is a clear benefit for tissue paper, but a damage to the thin paper you can use "the microalgae inside the pulp sheet.
    In a particular embodiment, Spirulina is used 15 for the microalgae in the base sheet of tissue paper. Spirulina has a high protein content and a relatively low carbohydrate content. In general, Spirulina has 60 to 70 percent protein, 15 to 25 percent carbohydrate, 4 to 7 percent fat and 4 to 7 percent fiber. One skilled in the art may find algae bioration not useful on paper due to the low amount of carbohydrates, and particularly cellulose, in the bioration. However, microalgae with a high protein content such as Spirulina can be used without loss of strength in the base sheet. Thus, the microalgae for use 25 with the tissue paper base sheet can have a protein content of more than 50 percent.
    Conventional papermaking fibers suitable for making tissue paper products contain any natural or synthetic cellulosic fibers, including, but not limited to, non-wood fibers, such as cotton, abaca, ke.na.-f, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed fibers and pineapple leaf fibers; and woody or pulp fibers, such as those obtained from deciduous and coniferous trees, including softwood fibers, such as 35 northern and southern softwood kraft fibers; and hardwood fibers, such as eucalyptus, maple, birch and poplar. Cellulose fibers can be prepared in high yield or low yield forms and can be pulped in any known method, including kraft, sulfite, high yield pulping methods and other known pulping methods. Fibers prepared from organosolv pulping methods can also be used, including the fibers and methods described in U.S. Patent No. 4,793,898 issued December 27, 1988 to Laamanen et al. ; U.S. Patent No. 4,594,130 issued June 1986 to Chang et al. ; and U.S. Patent No. 3,585 / 104, issued June 15, 1971 to Kleinert. 1úde'is fibers can also be produced by pulping with anthraquinone, exemplified by U.S. Patent No. 5,595,628 issued on January 21, 1997 to Gordon et al.
    A portion of the fibers, such as up to 50% or less by dry weight, or from about 5 to about 30 percent dry weight, may be synthetic fibers such as rayon, polyolefin fibers, polyester fibers, fibers bicomponent sheath-core, multi-component binding fibers and the like. An exemplary polyethylene fiber is Pulpex®, available from Hercules, Inc. (Wilmington, DE). Any known bleaching method can be used. Types of synthetic cellulose fiber include rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose. Chemically treated natural cellulosic fibers can be used such as mercerized pulps, chemically hardened or crosslinked fibers or sulfonated fibers. For good mechanical properties in the use of papermaking fibers, it may be desirable for the fibers to be relatively undamaged and largely unrefined, or only slightly refined. Although recycled fibers can be used, virgin fibers are generally useful for their mechanical properties - and the absence of contaminants. Mercerized fibers, regenerated cellulosic fibers, cellulose produced by microbes, rayon and other cellulosic materials or cellulosic derivatives can be used. Suitable papermaking fibers can also include recycled fibers, virgin fibers or mixtures thereof. In certain embodiments capable of high specific volume and good compression properties, fibers may have a Canadian Standard Freedom (Canadian Standard Freeness) of at least 200, more specifically at least 300, even more specifically at least 400 and more specifically at least 500. ■
    Other papermaking fibers may include broken or recycled paper fibers and fiber. -high yield. High-yield pulp fibers are those EiÈràs ■! ■! ** '■ ** papermaking products produced by pulping processes providing a yield of about 65 percent higher, more specifically around 75 percent or more, and even more specifically around 75 percent 95 percent. Yield is the resulting amount of processed fiber, expressed as a percentage of the initial wood mass. Such pulping processes include targeted chemothermomechanical pulp (BCTMP), chemothermomechanical pulp (CTMP), thermomechanical pressure / pressure pulp (PTMP), thermomechanical pulp (TMP), chemical thermomechanical pulp, high yield sulfite pulps and high yield kraft pulps , all of which leave the resulting fibers with high levels of lignin. High-performance fibers are known for their rigidity in both dry and wet states compared to typical chemically pulped fibers.
    In addition, the tissue paper product "can optionally include flocculating agents. The use of a dehydrating agent. * Flocculating can agglomerate the microalgae and make it easier. The retention of the microalgae within the tissue paper sheet. ...
    Exemplary flocculating agents can be selected from starches and modified starches (for example, cationic or amphoteric starch), cellulose ethers (for example, ‘carboxymethyl cellulose (CMC)) and their derivatives; alginates; cellulose esters; ketene dimers; succinic acid or anhydride polymers; natural gums and resins (especially manogalactans, for example, guar gum or locust bean gum) and the corresponding natural gums and modified resins (for example, cationic or amphoteric) (for example, modified guar gum); proteins (eg pop, cationic proteins), eg soy protein; polyvinyl alcohol); and polyvinyl acetate), especially partially hydrolyzed polyvinyl acetate). Flocculating agents, for the most part, also act to agglomerate microalgae. Cationic and amphoteric starches have been found to be particularly effective as a flocculating agent. Other particularly effective flocculating agents are polyvinylamines and polyvinylamines derivatives such as Catiofast® resins. and 5 Luredur®, manufactured and marketed by BASF such as, but not limited to, Luredur PR8095 and Catiofast VFH, Catiofast PR8Í236, Catiofast PR8104, Catiofast PR8102, Catiofast PR8087 and Catiofast PR8085.
    As mentioned above, flocculating agents 10 are used to agglomerate microalgae and make them easier to be retained within the tissue paper sheet. Although it is not desired to stick to any theory, it is believed that the flocculating agent becomes insoluble after binding to the loaded microalgae. The objective of agglomeration is to have the microalgae covered with bushy flocculating agent molecules. The starch molecules provide a cationic surface for the attachment of more microalgae, causing an increase in the size of the agglomerate and increasing the ability of algae to be retained in the web.
    The size of the starch-microalgae clusters is an important factor in achieving the ideal balance of resistance and optical properties. The size of the agglomerate is controlled by the shear rate provided during mixing - ■ * '••' I V.I of the starch with the pulp suspension. The agglomerates, once formed, are not excessively sensitive to shearing., But they can be broken for an extended period of time or ... in the presence of very high shear forces. In particular, such high shear forces can be found in the fan pump that feeds the diluted pulp suspension to the tissue paper machine's inbox.
    The characteristic charge of the flocculating agent is also significant. For example, starch is generally used in an amount less than 5 weight percent of microalgae; ... the microalgae-starch agglomerates still have a net negative charge 35. In this case, a cationic retention aid is used. In other cases, it may be beneficial to use an anionic or amphoteric retention aid.
    Various cationic retention aids are known in the art. In general, the most common cationic retention aids are charged polyacrylamides. These retention aids agglomerate the suspended particles through the use of a binding mechanism. A wide range of molecular weights and charge densities are available. In general, high molecular weight materials with a medium charge density are preferred for flocculation of microalgae. The retaining adjuvant flakes are easily broken by shear forces and are therefore usually added after the fan pump that supplies the diluted pulp suspension to the tissue box inlet box.
    Examples of cationic polymeric retention aids are polydialyldimethylammonium chlorides (polyDADMAC) and branched polyacrylamides, which can be prepared, for example, by copolymerization of acrylamide or methacrylamide with at least one cationic monomer in the presence of small amounts of crosslinking agents.
    Suitable cationic retention aids are polyamines with a molar mass greater than 50,000, modified polyamines that are grafted with ethylenimine and, if necessary, polyvinylpyrrolidines, hydropyrines, crosslinked, polyvinylimidazoles, polyvinylimidazolines, polyvinyl tetra. > •, ■! poly (dialkylaminoalkylvinylethers), poly (dialkylaminoalkyl (meth) acrylates) in the protonated or quaternized form and polyamidoamines obtained from a dicarboxylic acid, such as adipic acid, and polyalkylene polyamines, such as diethylenetriamine, which are grafted with ethylene hydroxide and ethylene hydroxide and retained with ethylene hydroxide , which react with epichlorohydrin to produce water-soluble condensates. Additional retention aids are cationic starches, alum and polyaluminium chloride.
    Base sheets of tissue paper that can be used to build the tissue paper product, for example, can generally contain cellulose fibers alone or in combination with other fibers. Each tissue paper web generally has an apparent density of at least 2 cm3 / g, such as at least 3 cm3 / g and, more typically, at least 4 cm3 / g.
    The tissue paper products of the present invention can be single layer or multilayer. Base sheets of tissue paper may include a single homogeneous layer of fibers, called a combined base sheet, or may include a stratified or layered construction, wherein the layer of the base tissue sheet may include two or three layers fiber extracts. Each layer can have a different fiber composition. Microalgae can be selectively located in one or several layers or can be located in all layers of the layered base sheet.
    The basis sheet weight used for the individual layers comprising the tissue paper product may vary depending on the final product. For example, the process can be used to produce facial tissue papers, toilet papers, paper towels, industrial tissues and the like. In general, the weight of the base sheet or the individual layer of tissue paper products can vary from about 5 to about 120 g / m2, such as from about 7 to about 80 g / m2. For toilet and facial papers, for example, the weight of the individual layers comprising the tissue paper product can vary from about 7 to about 60 g / m2. For paper towels, on the other hand, the weight can vary from about 10 to about 80 g / m2.
    In products with multiple layers, the weight of each tissue paper web present in the product can also vary. In general, the total weight of a product with multiple layers will generally be the same as indicated above multiplied by the number of layers. In particular, the multilayer products of the present invention can have weights such as from about 15 to about 100 g / m2. Thus, the weight of each layer can be from about 5 to about 100 g / m2, such as from about 7 to about 50 g / m2.
    In general, the tissue paper sheet can be formed using any suitable papermaking techniques. For example, a papermaking process may use creping, wet creping, double creping, embossing, wet compression, air compression, air drying, crepe air drying, un-crepe air drying, hydro-entanglement, deposit air, as well as other steps known in the art.
    Such an exemplary technique will be described later in this document. A wet end reserve system that could be used in the manufacture of a tissue paper product is illustrated in Figure 1. The wet end reserve system includes a chest (15) for storing a combination of aqueous suspension of paper-making fibers and microalgae. A cationic flocculating agent can generally be employed to flocculate microalgae in an amount. When used, cationic starch can be added up to about 5 weight percent of microalgae, and more desirably about 3 weight percent of microalgae. From the container 15, the fiber-water suspension enters the material box 16 used to maintain a constant pressure head. Generally, the entire outlet of the material box 16 is sent through the outlet flow 18 to a fan pump 20.
    Alternatively, however, a portion of the outflow 17 from the material box 16 can be removed as a separate flow and sent to the fan pump 20, while the remaining portion can be recirculated back to the material box 16, as described in US Patent No. 6,027,611 to McFarland 25 et al., which is incorporated herein by reference in this document.
    The retention aid can be added at any point between the container 15 and the inbox 24 (Figure 2), for example, the addition point 26, shown in Figure 2. Desirably, the retention aid is added in 30 an outlet side of the fan pump 20 of the container. The cationic retention aid is added to improve the retention of microalgae. When used, the retention aid is usually added after the fan pump at a level of 48 to 680 g (0.1 to 1.5 pounds) per metric ton of dry fiber,
    A schematic process flow chart of the machine used to manufacture a sized tissue paper product is illustrated in Figure 2. The machine includes the inbox 24 que! receives the discharge or outlet flow 22 from the fan pump 20 and continuously injects or deposits the aqueous paper fiber suspension into an internal forming tissue 30 as it travels through a forming cylinder 31. An external forming tissue paper 32 5 serves to contain the web as it passes over the forming cylinder 31 and spills some of the water. The wet web 34 is then transferred from the internal forming fabric 30 to a wet end transfer fabric 36 with the aid of a vacuum transfer shoe 38. This transfer is preferably carried out with the transfer 36 moving at a slower speed than the internal forming tissue 30 (rapid transfer) to impart stretch to the final tissue paper product. The wet web 34 is then transferred to the directly dried fabric 40 with the aid of 15 a vacuum transfer cylinder 42. The directly dried web 40 carries the wet web 34 over the direct dryer 44, blowing hot air in the web 34 to dry it while preserving the specific volume. Optionally, there can be more than one direct dryer in series (not shown), depending on the speed and capacity of the dryer. The dry tissue paper sheet 46 is then transferred to a reel drum 48 directly from the directly dried tissue 40. The transfer is carried out by vacuum suction from inside the reel drum 48 and / or by pressurized air . The tissue paper sheet 46 is then rolled into a 25 cylinder 50 on a 52 roll. US Patent No. 5,591,309, to Rugowski et al., Which is incorporated by reference in this document, describes equal and additional techniques for direct drying of a wet formed sheet, according to US Patent Nos. 5,399,412 to Sudall et al. and 5,048,589 for Cook et al., both of which 30 are also incorporated by reference in this document.
    The tissue paper product can be a high specific volume material. The specific volume of the tissue paper product can vary between about 2 to about 25 cm3 / g, more specifically between about 3 to about 20 cm3 / g, and even more specifically 35 between about 4 to about 18 cm3 / g.
    The caliber of single layer tissue paper can be at least about 60 micrometers or greater, and is desirably about 90 to about 1,200 micrometers' 'and particularly about 120 to about 1,000 micrometers.' Likewise, the gauge of the tissue paper products of the present invention can vary from about 90 to about 1,500 micrometers as well as from about 120 to about 1,200 micrometers.
    The tissue paper product and tissue paper base sheet described here may have a specific absorbent capacity expressed as grams of water absorbed per gram of fiber, from about 6 g / g or greater, between about 7 to about 18 g / g, or between about 8 to about 16 g / g.
    The tissue paper product described in this document may have a geometric mean tensile strength expressed in grams (strength) per 3 inches of sample width of about 52.5 g / cm (400 g / 3 ") or greater, or between ceffea from 78.7 to about 590.6 g / cm (about 600 to about 4500 g / 3 "). TEST METHODS Grammage
    The weight and the very dry weight of tissue paper sheet samples are determined using the TAPPI T410 procedure or a modified equivalent, such as: Tissue paper samples are conditioned at 23 ° C ± 1 ° C and 50 ±, 2 percent relative humidity for a minimum period of 4 hours. After conditioning a stack of 16 7.62 cm x 7.62 cm (3 inches by 3 inches) samples, the samples are cut using mold pressing and the associated mold. This represents a tissue sample area of 144 inches or 929 cm2. Examples of suitable mold presses are the TMI DGD mold press manufactured by Testing Machines, Inc., Iceland, NY, or a Swing Beam test machine manufactured by USM Corporation, Wilmington, MA. The dimensional tolerances of the mold are ± 0.02 cm (± 0.008 inch) in both directions. The sample stack is then weighed with an accuracy of 0.001 g on a tared analytical balance. Weight in grams per square meter is calculated using the following equation: weight = weight of the pile in grams / 0.0929. Geometric Average of Tensile Strength
    For the purposes of this document, tensile strength can be measured with a Sintech tensile gauge using a 7.62 cm (3 inch) jaw width (sample width), a 5.08 cm (2 inch jaw extension) ) 5 (meter length) and a crosshead speed of 25.4 centimeters per minute after keeping the sample under TAPPI conditions for 4 hours before testing. "MD tensile strength" is the peak load per 7.62 cm (3 inches) of sample width when a sample is pulled until it breaks in the machine direction *. '
    Likewise, the "CD tensile strength" represents the peak load per 7.62 cm (3 inches) of sample width when a sample is pulled to rupture in the transverse direction of the machine. The geometric mean of tensile strength (GMT) is the square root of the product of the tensile strength in the machine direction and the tensile strength in the transversal direction of the weft machine. The "CD resistance" and "MD resistance" are the amount of elongation of the sample in the machine's transverse direction and in the machine direction, respectively, at the breaking point, expressed as a percentage of the initial sample length.
    More particularly, the samples for tensile strength tests are prepared by cutting strips. '3. inches (76.2 mm) wide by at least 4 inches (101.6 mm) long in machine direction (MD) or machine cross direction (CD) using a JDC precision sample cutter (Thwing-Albert Instrument Company, Philadelphia, PA, Model No. JDC 3-10, Serial No. 37333). The instrument used to measure tensile strength is Sintech from MTS Systems Serial No. 1G / 071896/116. The data acquisition software is MTS TestWorks® for Windows version 4.0 (MTS Systems Corp., Eden Prairie, MN). The load cell is an MTS maximum 25 Newtons load cell. The measurement length between the mandibles is 2 ± 0.04 inches (76.2 + 1 mm). The jaws are operated using pneumatic action and are coated with rubber. The width of the minimum gripping face is 3 inches (76.2 mm) and the approximate height of a jaw is 0.5 inches (12.7 mm). The burst sensitivity is set at 40 percent. The sample is placed in the instrument's jaws and centered both vertically and horizontally. To adjust the initial clearance, a preload of 1 gram (force) at the rate of 0.25 cm (0.1 inch) per minute is applied for each test performed. 'The test is then started and ends when the strength drops by 40% 'from the peak 5. The peak load is recorded as the "MD tensile strength" or the "CD tensile strength" of the sample, depending on the sample being tested. At least 3 representative samples are tested for each product, taken "as-is", and the arithmetic mean of all individual ampule tests 10 is the MD or CD tensile strength for the product; .
    As used here, the "geometric mean," '' tensile strength "is the square root of the MD tensile strength product multiplied by the CD tensile strength, both as determined above, expressed in grams (strength) by 3 15 inches sample width. Specific Caliber and Volume
    The specific volumes of the base sheet and the individual sheets that make up the multilayer product may or may not be the same. However, the tissue paper products 20 of the present invention will have a specific volume greater than about 2 cubic centimeters per gram or more, and more specifically, from about 3 to about 24 cubic centimeters per gram, more specifically about from 4 to about 16 cubic centimeters per gram.
    The specific volume of a single sheet is calculated by taking the gauge of the single sheet and dividing it by the conditioned weight of the product. The term "gauge", as used herein, is the thickness of a single sheet of tissue paper, "" ê can be measured as the thickness of a single sheet of tissue paper 30 or as the thickness of a stack of ten sheets of tissue. 'tissue paper and dividing the sheet thickness of ten fabrics by ten, where each sheet inside the stack is placed with the same side up.
    As used here, the "gauge" of the sheet is the representative thickness of a single sheet, measured according to the TAPPI T402 test methods "Standard Conditioning and Testing Atmosphere For Paper, Board, Pulp Handsheets and Related Products" and T411 om -89 "Thickness (caliper) of Paper, Paperboard, and Combined Board" with Note 3 for stacked sheets. The micrometer used to perform the T411 om-89 is an Emveco 200-A Tissue Paper Gauge Tester, available from Emveco, Inc., 5 Newberg, OR. The micrometer has a load of 2 kilopascals, an area of the pressing foot of 2500 square millimeters, a diameter of the pressing foot of 56.42 mm, a dwell time of 3 seconds and a reduction rate of 0.8 mm per second.
    As used here, the "specific volume" of the sheet: 10 is calculated as the quotient of the "gauge", expressed in micrometers, divided by the dry weight, expressed in grams per square meter. The specific volume of the resulting sheet is expressed as cubic centimeters per gram. Mud
    To determine the abrasion resistance or tendency of fibers to be scraped in the web when handled, each sample was measured by abrasion of the tissue paper samples using the method as is further described in US Patent No. 6,861,380, to Garnier et al . , incorporated herein by reference. This test measures the resistance of the tissue paper material to abrasive action when the material is subjected to a horizontally alternative surface abrasor. All samples were conditioned at 23 ° C ± 0.1 ° C and 50 percent ± 0.2 percent relative humidity for a minimum of 4 hours.
    The abrasion spindle contained a stainless steel rod, 1.27 cm (0.5 inch) in diameter, with the abrasive portion consisting of a diamond pattern of 1, 2-7 mm (0.005 inch) deep if extending 10 ', 8. cm (4.25 inches) long around the entire circumference 30 of the stem. The spindle was mounted perpendicular to the facet of the instrument, so that the abrasion portion of the stem extends out all its distance from the face of the instrument. On each side of the spindle were guide pins with magnetic clamps, one movable and the other fixed, spaced 10.2 cm (4 inches) from each other and centered around the spindle. The movable clamp and guide pins were allowed to slide freely in the vertical direction, the weight of the jaw providing the means to ensure constant sample tension on the spindle surface.
    Using in-mold pressing with a mold cutter, samples were cut into strips 7.6 ± 0.1 cm 5 (3 inches ± 0.05 inch) wide by 20.3 cm (8 inches) long with two holes at each end of the sample. For tissue paper samples, the MD direction corresponds to the longest dimension. Each test strip was then weighed to the nearest 0.1 mg. Each end of the sample was slid 10 over the guide pins and magnetic clamps fixed the sheet in place. The movable jaw was then dropped, providing constant tension for the spindle. The spindle was then moved back and forth at an approximate angle of 15 degrees from the vertical center line 15 centered in a reciprocal horizontal movement against the test strip for 20 cycles (each cycle is a back and forth stroke), at a speed of 80 cycles per minute, removing loose fibers from the weft surface. Additionally, the axis was rotated counterclockwise (when looking at the front of the instrument) at an approximate speed of 5 RPM. The magnetic clamp was then removed from the sample and the sample was slid off the guide pins and any loose fibers on the sample surface were removed by blowing compressed air (approximately 34.5 to 68.9 kPa (5 to 10 psi)) on the 25 test sample. The test sample was then weighed with an accuracy of 0.1 mg and the weight loss was calculated. Ten test samples per tissue sample were tested and the average weight loss value in milligrams was recorded. Absorption Capacity
    A 10.2 cm x 10.2 cm (4 inches by 4 inches) sample is initially weighed. The heavy sample is then soaked in an autoclave (pan) of test fluid (for example, in paraffin oil or water) for three minutes. The test fluid should be at least 2 inches (5.08 cm) deep 35 in the autoclave. The sample is removed from the test fluid and allowed to drain while being hung in a "diamond" position (ie with a corner at the lowest point). The sample is allowed to drain for three minutes into the water and for five minutes into the oil. After the assigned flow time, the sample is placed on a weighing plate and is then weighed. The absorption capacity of acids or bases, with a viscosity 5 more similar to water, is tested according to the procedure for testing the absorption capacity for water. Absorption Capacity (g) = wet weight (g) - dry weight (g); and Specific Absorption Capacity (g / g) = Absorption Capacity (g) / dry weight (g) ■ EXAMPLE
    The present invention can be better understood with reference to the following example. For Examples 1 to 3, a combination of conventional papermaking fibers and microalgae was prepared. Eucalyptus 15 hardwood fibers commercially available from Fibria, São Paulo, Brazil were used. Spirulina algae were obtained as "Natural Spirulina Powder", commercially available from Earthwise Nutritionals, Calipatria, CA, USA. In examples 1 to 3, a base sheet of directly woven, non-creped paper with three 20 single-layer layers was generally made according to U.S. Patent No. 5,607,551, to Farrington et al. which is incorporated by reference.
    More specifically, 29.5 kg (65 pounds) (kiln dried base) of eucalyptus hardwood kraft fiber were dispersed in a pulper for 25 minutes at a consistency of 3 percent before being transferred in equal parts to 'two machine containers and diluted to a 1 percent consistency. When in use, the algae were added as a dry powder in equal amounts to each machine container. The 30 seaweeds were added over a period of 5 minutes to avoid agglutination and were then dispersed for an additional 5 minutes in the machine container before adding starch, if used. An amphoteric starch, Redibond 2038A, available as a 30% aqueous active solution from National 35 Starch and Chemical, was used. The appropriate amount of starch to be added was determined from the amount of eucalyptus in each machine container. The appropriate amount of starch was weighed and diluted to a 1% active solution with water before being added to the machine container. When algae were used, the starch was added after the addition of the algae.4. The fiber paste was mixed for 5 minutes before the stock solution 5 was sent to the headbox, 18 , 1 kg (40 pounds) (kiln dried base) of northern softwood kraft fiber was dispersed in a pulper for 25 minutes at a 3 percent consistency before being transferred to a second machine container and 10 diluted to 1 percent consistency. Softwood fibers can be refined after pulping and before transfer to the machine container, as noted in the examples.
    Prior to formation, each stock was further diluted to approximately 0.1 percent consistency and transferred 15 to a 3-layer inbox to provide a layered sheet comprising 65% eucalyptus and 35% NSWK, in that the outer layers comprised eucalyptus / algae combination and the inner layer comprised NSWK fibers. A solution of an average molecular weight cationic retention aid, 20 Praestol 120L, available from Ashland Chemical, was prepared by adding 80 grams of Praestol 120L, as received, to 80 liters of water, under high shear agitation. The diluted solution was added in line to the pump outlet side of the fan for each flow of eucalyptus pulp, since the diluted pulp suspension moved to the inbox at a rate of about 0.035 to 0.040 per weight percent of fiber.
    The web formed was then dehydrated in a non-compressive mod and quickly transferred to a transfer fabric, moving at a speed 25 percent slower than the fabric in formation. The weft was then transferred to a direct drying, dried and calendered fabric. The weights of the inner and outer layers were determined individually to ensure that a 32.5 / 35 / 32.5 layer division is maintained.
    Several comparative examples have been prepared to illustrate the effect of adding microalgae, a retention aid and starch, as described above. Comparative Example 1 was prepared only with eucalyptus and NSWK fibers. Comparative Example 2 was prepared only with eucalyptus fibers and microalgae. Comparative Example 3 was prepared only - with eucalyptus fibers, microalgae and starch. Comparative Example 4 was prepared only with eucalyptus and starch fibers. Comparative Example 5 was prepared only with eucalyptus starch and a retention aid. The color of the base sheet was observed. The higher degree of green color observed indicates that more algae are retained on the leaf. Thus, Examples 1, 2 and 3 containing microalgae, a flocculating agent and a retention aid, retained the largest amount of microalgae in the tissue paper sheet.
    Likewise, surprisingly, despite the introduction of very small algae particles, reductions in mud are achieved. Table 1
    Table 2 provides a summary of the results of the specific test in the base sheet. The results at Tàbelá - <- 2 show that the inclusion of microalgae, a retention aid and a flocculating agent has a significant impact on increasing the specific volume and the specific water absorption capacity, while maintaining a low sludge and high air permeability. As illustrated by comparative example 5, the increase in specific volume and water absorption capacity is above and beyond what is experienced from the addition of only starch to the retention aid. Tablea 2
    Having described the invention in detail, it will be evident that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. ,
    权利要求:
    Claims (15)
    [0001]
    1. Tissue paper base sheet (46) comprising: a combination of conventional papermaking fibers and microalgae; and an ionic retention aid; said tissue paper product comprising from 1 to 50 percent based on the total weight of the microalgae tissue paper product, characterized by further comprising a flocculating agent.
    [0002]
    2. Tissue paper base sheet (46), according to claim 1, characterized by the fact that microalgae is a biofuel of algae biofuel production.
    [0003]
    3. Tissue paper base sheet (46) according to claim 1 or 2, characterized in that the flocculating agent comprises an amphoteric or cationic starch.
    [0004]
    4. Tissue paper base sheet (46) according to any one of claims 1 to 3, characterized in that it comprises less than 5 percent of the flocculating agent based on the weight of the microalgae.
    [0005]
    5. Tissue paper base sheet (46) according to any one of claims 1 to 4, characterized in that the flocculating agent comprises a polyvinylamine or derivative thereof
    [0006]
    6. Tissue paper base sheet (46) according to any one of claims 1 to 5, characterized by the fact that microalgae are selected from non-mobile, flagellate, diatomous and blue-green algae.
    [0007]
    7. Tissue paper base sheet (46) according to any one of claims 1 to 6, characterized in that it comprises between 10 and 40 percent based on the total weight of the microalgae tissue paper product, and preferably comprises between 10 and 30 percent based on the total weight of the microalgae tissue paper product.
    [0008]
    8. Tissue paper base sheet (46) according to any one of claims 1 to 7, characterized in that the retention aid comprises a cationic retention aid selected from polydialldimethylammonium chlorides and branched polyacrylamides
    [0009]
    9. Tissue paper base sheet (46) according to any one of claims 1 to 8, characterized in that the tissue paper product has a specific absorbent capacity of 8 g / g or greater; and / or where the tissue paper product has a volume of 4 to 18 cm3 / g; and / or where the tissue paper product has a geometric mean of tensile strength greater than 500 g / 3 ".
    [0010]
    10. Tissue paper product, characterized by comprising one or more layers of the tissue paper base sheet (46) as defined in any one of claims 1 to 9.
    [0011]
    11. Tissue paper product according to claim 10, characterized by the fact that the tissue paper product is a toilet paper, tissue paper, paper towel or napkin.
    [0012]
    12. Method of preparing the tissue paper base sheet (46), as defined in any one of claims 1 to 11, in a wet-end reserve system that includes a container (15) and an inlet box (24) , characterized by understanding: combining fibrous material from microalgae with conventional papermaking fibers in a wet state to produce a combination of microalgae / papermaking fibers; adding a retention aid to the combination of microalgae / papermaking fibers between the container (15) and the inbox (24); drying the weft to form a base sheet of tissue paper; wherein the method further comprises the steps of adding a flocculating agent to the container.
    [0013]
    13. Method according to claim 12, characterized by the fact that microalgae are bioration of algae biofuel production.
    [0014]
    Method according to claim 12 or 13, characterized by the fact that the retention aid is added to an outlet flow (18) from a pump (20) of the container fan.
    [0015]
    15. Tissue paper base sheet according to any one of claims 1 to 11, or the method according to any of claims 12 to 14, characterized by the fact that the tissue paper base sheet has a base weight of 7 to 60 gsm and a volume of 2 cm3 / g to 25 cm3 / g.
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    同族专利:
    公开号 | 公开日
    WO2011154855A3|2012-04-12|
    US20110303375A1|2011-12-15|
    AU2011263363A1|2012-11-29|
    EP2580392A2|2013-04-17|
    WO2011154855A2|2011-12-15|
    EP2580392A4|2014-08-06|
    CA2799302C|2016-10-11|
    EP2580392B1|2016-07-06|
    IL222917A|2016-12-29|
    AU2011263363B2|2015-01-22|
    MX2012013542A|2013-01-24|
    BR112012030321A2|2016-08-09|
    CA2799302A1|2011-12-15|
    KR20130131212A|2013-12-03|
    US8298374B2|2012-10-30|
    KR101470722B1|2014-12-08|
    IL222917D0|2012-12-31|
    ZA201208411B|2014-01-29|
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    法律状态:
    2019-02-26| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-12-31| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-05-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US35374510P| true| 2010-06-11|2010-06-11|
    US61/353,745|2010-06-11|
    US12/972,767|2010-12-20|
    US12/972,767|US8298374B2|2010-06-11|2010-12-20|Tissue products containing microalgae materials|
    PCT/IB2011/051961|WO2011154855A2|2010-06-11|2011-05-03|Tissue products containing microalgae materials|
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