专利摘要:
The invention relates to polymeric hydroxyl polymer structures, for example, fibrous elements, such as filaments and / or fibers, and more particularly fibrous elements of hydroxylated polymer which contain a dual-use material and / or a component of dual-use material, fibrous structures made therefrom, and methods for their manufacture.
公开号:FR3017391A1
申请号:FR1551040
申请日:2015-02-10
公开日:2015-08-14
发明作者:Stephen Wayne Heinzman；Jeffrey Allen Bowles
申请人:Procter and Gamble Co；
IPC主号:

专利说明:

[0001] The present invention relates to polymer structures of hydroxylated polymers, for example, fibrous elements, such as filaments and / or fibers, and / or to polymeric structures of hydroxylated polymers, for example fibrous elements, such as filaments and / or fibers, and more particularly hydroxyl polymer fibrous elements which comprise a dual-use material and / or a dual-use material component, fibrous structures made therefrom, and methods for their manufacture.
[0002] BACKGROUND OF THE INVENTION Polymeric hydroxyl polymer structures, such as fibrous elements, produced from hydroxyl crosslinking polymers are known in the art. It is known to crosslink hydroxylated polymers together by means of a crosslinking agent, such as a dihydroxyethylene-urea (DHEU), in combination with a crosslinking aid which prevents unacceptable crosslinking of the polymers. hydroxylated by the crosslinking agent occurs. The challenge of managing the crosslinking of hydroxylated polymers is especially problematic when spinning fibrous elements from an aqueous hydroxyl polymer molten composition.
[0003] Ammonium salts, such as ammonium chloride, ammonium sulfate and ammonium citrate, are known to act as crosslinking aids in aqueous compositions of molten hydroxyl polymer. Such ammonium salts are initially inactive crosslinking agents (catalysts) in aqueous molten hydroxyl polymer compositions, but become active acid catalysts during heating of an embryonic polymer structure formed from the aqueous polymer composition. hydroxylated during a hardening step. The problem with such ammonium salts, which are cosmotropic salts, such as ammonium sulfate and / or ammonium citrate, in the aqueous hydroxyl polymer composition melted at the rate necessary to complete the cure during The curing step is that they can cause release of the hydroxylated polymer, which results in weaker polymer structures formed therefrom during the polymer treatment step. Another negative aspect that results from the addition of ammonium salts, such as ammonium chloride, ammonium sulfate and ammonium citrate, is the increased absorption of water from the storage of polymeric structures. in humid conditions. This results in a change in the tensile properties of the polymeric structures as a function of the atmospheric environment, which is undesirable for consumer products, such as toilet paper products, utilizing the polymeric structures.
[0004] In addition to the negative aspects previously discussed, the presence of ammonium sulfate in the aqueous hydroxyl polymer melt compositions lowers the critical micelle concentration (CMC) of any fast wetting surfactants, such as sulfosuccinate diester salts. of sodium, present in the aqueous hydroxyl polymer melt compositions, which, in turn, decreases the wetting ability of fast wetting surfactants. This decreased wetting capacity limits the ability of fast wetting surfactants to increase the drying of polymeric structures formed from the aqueous molten hydroxyl polymer compositions. This ultimately results in negative aspects in the fibrous elements, for example, increased diameters of the fibrous elements formed from the molten hydroxylated aqueous polymer composition. In addition, ammonium carboxylic salts, such as ammonium citrate, intolerably buffer the pH of the precured polymeric structure to a pH greater than 5, which prevents complete cross-linking of the hydroxylated polymers from occurring during the course of time. hardening step.
[0005] Finally, other salts, such as ammonium chloride, tend to also impart an undesirable yellow color to the polymeric structure during the high temperature of the curing step. In addition, ammonium chloride causes corrosion of the processing equipment used to make the polymer structure. In light of the foregoing, currently used crosslinking agents do not facilitate sufficient crosslinking of the hydroxylated polymers present in an aqueous hydroxyl polymer composition melt during the production of the polymeric structures to provide polymeric structures with acceptable physical properties, such as as resistance, and color properties.
[0006] Formulators of non-aqueous polymeric compositions such as useful non-aqueous polymeric coating compositions, such as automotive refinishing products, have used ammonium sulfosuccinate diester salts as an acid catalyst to activate the crosslinking agents. amino resin to produce a non-aqueous film coating. Nowhere, however, do formulators of such nonaqueous polymeric coating compositions teach or suggest using such ammonium sulfosuccinate diester salts in aqueous hydroxylated polymer compositions, especially for making fibrous elements, such as filaments from such aqueous hydroxyl polymer compositions melted. Another problem is encountered in cases where the fibrous elements are produced from aqueous polymer compositions, for example, aqueous hydroxylated polymer compositions comprising hydroxylated polymers, such as polysaccharides. Hot drying air is used to remove water from the aqueous hydroxyl polymer compositions melt during spinning to produce the fibrous elements, which can be collected to form a fibrous structure. The removal of water from the emerging fibrous elements helps to prevent the fibrous elements from sticking together during the spinning and / or collecting processes. The inability to effectively remove water from the fibrous elements during formation results in relatively poor tensile properties, such as relatively lower ultimate tensile strength (FS), relatively lower total dry tensile strength (TDT). and / or a relatively lower total absorbed energy (TEA) in fibrous structures produced from inefficiently dried fiber elements. It is believed that these poor tensile properties in the fibrous structure are caused, at least in part, by excessive bonding of the fibrous elements to one another, which occurs when the fibrous elements are not effectively dried. However, the use of larger amounts of drying air is economically unfeasible and consumes a lot of energy. In addition, dry, ineffectively dried fibrous elements have relatively larger average diameters, which impact various properties of the fibrous structures produced therefrom. In the past, formulators have combined a crosslinking agent, such as DHEU, with simple salts, such as ammonium chloride (NH4Cl), and a fast wetting surfactant, such as the sodium sulfosuccinate diester salt. sodium, in an aqueous hydroxyl polymer composition melted to produce filaments. It has been unexpectedly found that filaments spun from such an aqueous hydroxyl polymer molten composition and / or a web formed from the filaments have a salt content as represented by their conductivity as measured by The conductivity test method described herein which is higher than desired (i.e. greater than 130 microsiemens) for consumer products, for example, sanitary tissue products. Thus, a problem encountered by the formulators of hydroxyl polymer polymer structures from aqueous hydroxyl polymer melt compositions is the reduction of the level of salts (i.e., non-sulfosuccinate diester salts), such as ammonium chloride and / or sodium chloride and / or other simple salts previously thought to be necessary to facilitate cross-linking through a crosslinking agent present in polymeric structures of hydroxylated polymer without negatively impacting the ability of the hydroxyl polymer polymer structures to be dried (for example, to remove water therefrom). Thus, a need for a dual-use material exists, for example, an ammonium sulfosuccinate diester salt and / or iminium, which performs both a crosslinking agent function and a function. fast wetting surfactant composition in an aqueous hydroxyl polymer melt composition, which is spun into fibrous elements, such as filaments, while at the same time eliminating the need for additional salts, such as ammonium and / or sodium chloride, which are present in the aqueous hydroxyl polymer melt composition and / or the fibrous elements produced therefrom as additional crosslinking agents.
[0007] SUMMARY OF THE INVENTION The present invention satisfies the previously described requirements by providing an aqueous molten hydroxyl polymer composition comprising a dual-use material that has both a crosslinking agent (catalyst) and an agent function. fast wetting surfactant (wetting), for example, an ammonium and / or iminium sulfosuccinate diester salt, a polymeric structure, for example, a fibrous element, made therefrom, a formed fibrous structure from it and a method of manufacturing such a fibrous element and / or such a fibrous structure. A solution to the previously identified problem is to incorporate a dual-use material which has both a crosslinking agent (catalyst) function and a fast wetting surfactant (wetting) function, e.g. ammonium and / or iminium sulfosuccinate diester in an aqueous hydroxyl polymer composition melt such that the dual-use material and / or the dual-use material component (s) cause the following: 1) the water of the fibrous elements formed from the molten hydroxylated aqueous polymer composition is more effectively removed without increasing the rate of drying air used to form the fibrous elements (evidence of fast wetting surfactant function) ), 2) the salting out of the hydroxylated polymers does not occur in the molten hydroxylated aqueous polymer composition before the crosslinking of the hydroxylated polymers within the hydroxylated polymer. polymer structure, for example, fibrous elements, occurs in a curing step and thus forming the polymer structure, for example, a fibrous element (evidence of the attenuation of the salt level), 3) the hydroxylated polymer is not crosslinked prior to the polymer treatment step (evidence of the crosslinking promoting agent function), 4) the polymer structure is effectively crosslinked during the curing step to provide the polymeric structure with acceptable physical properties, such as resistance, both dry and wet (evidence of the function of crosslinking promoting agent), and / or 5) the cured polymer structure has an acceptable color (not yellow) (evidence of attenuation of additional salts ). A first object of the invention is a fibrous element comprising a fibrous element forming polymer and a dual-use material, wherein the dual-use material has both a crosslinking agent function and a crosslinking function. fast wetting surfactant. The fibrous element of the present invention may comprise a fibrous element forming polymer which comprises a hydroxylated polymer. Preferably, said hydroxylated polymer comprises a polysaccharide. More preferably, said polysaccharide is selected from the group consisting of: starch, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives, cellulose copolymers, hemicellulose, derivatives thereof hemicellulose, hemicellulose copolymers, and mixtures thereof.
[0008] The fibrous element of the present invention may comprise a crosslinking agent which is selected from the group consisting of: imidazolidinones, polycarboxylic acids and mixtures thereof. Preferably, said crosslinking agent comprises an imidazolidinone. More preferably, said imidazolidinone is dihydroxy-ethylene-urea. The fibrous element of the present invention may comprise a dual-use material which comprises one or more of the following compounds: a. an ammonium sulfosuccinate diester salt; b. an iminium sulfosuccinate diester salt; and c. their combinations. The fibrous element of the present invention may comprise a dual-use material which has the following Formula I: ## STR3 ## wherein MO 3 S is M + and -O 3 S, where M 1 is an ammonium or iminium cation, e.g. NHnR24_n where n is from 0 to 4 and / or from 0 to 3 and / or from 0 to 2 and / or from 0 to 1 and / or is equal to 0; and R2 is independently selected from the group consisting of: alkyl, hydroxyalkyl, alkanolamine, aryl, hydroxylaryl, or part of a heterocyclic ring, and wherein R is linear or branched C1-C18 alkyl and / or linear alkyl or branched C1 to C12 and / or linear or branched C1 to C8 alkyl. Preferably, said R2 is an aliphatic or aromatic N-heterocycle. The fibrous element of the present invention may comprise a dual-use material which is produced from an amine and a sulfosuccinic acid diester.
[0009] Preferably, said amine has a boiling point of less than 270 ° C. The fibrous element of the present invention may comprise a dual-use material which is selected from the group consisting of: bis (bisobutyl ester) sulfosuccinic acid ammonium salt; ammonium salt of sulfosuccinic acid bis (pentyl ester); sulphosuccinic acid bis (2-ethylhexyl ester) ammonium salt wherein the ammonium cation is derived from ammonia, dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, 2-amino-2-methyl-1-propanol, methyldiethanolamine, 4-methylmorpholine, 4-methylmorpholine, 4,4-dimethyloxazolidine. The fibrous element of the present invention may further comprise a non-hydroxylated polymer which is selected from the group consisting of: polyacrylamide and its derivatives; polyacrylic acid, polymethacrylic acid and their esters; polyethyleneimine; copolymers made from monomer mixtures of the aforementioned polymers; and their mixtures. Preferably, said non-hydroxylated polymer comprises a polyacrylamide. The fibrous element of the present invention may comprise a filament.
[0010] The fibrous element of the present invention may have an average diameter of less than 50 μm as measured by the average diameter test method. The fibrous element of the present invention may be made from an aqueous molten hydroxyl polymer composition comprising the fibrous element forming polymer, the crosslinking agent, and the dual-use material.
[0011] Another subject of the invention is a fibrous structure comprising a plurality of fibrous elements according to the invention. The fibrous structure of the present invention may further comprise one or more solid additives. Preferably, at least one of said solid additives comprises a naturally occurring fiber.
[0012] The fibrous structure of the present invention may further comprise a scrim attached to the surface of the fibrous structure such that the solid additives are positioned between the scrim and a surface of a nonwoven substrate of the fibrous structure. Another object of the present invention is a method of manufacturing a fibrous structure comprising the steps of: a. providing an aqueous molten hydroxyl polymer composition comprising a fibrous element forming polymer and a crosslinking system comprising a crosslinking agent and a dual-use material which has both a crosslinking agent function and a crosslinking function. fast wetting surfactant; and B. performing a polymer treatment of the aqueous hydroxyl polymer composition melt so that a plurality of fibrous elements the invention is formed; vs. collecting the fibrous elements on a collection device such that a fibrous structure is formed. In one example of the present invention, there is provided a polymeric structure, for example a fibrous element, comprising a mixture comprising a fibrous element-forming polymer, such as a hydroxylated polymer, for example a crosslinked hydroxylated polymer, and one or more dual-use materials and / or dual-use material components, for example, an ammonium and / or iminium sulfosuccinate diester salt and / or its sulfosuccinic acid and / or diester ions and or ammonia and / or an amine.
[0013] In another example of the present invention, there is provided a fibrous structure comprising a plurality of fibrous elements of the present invention. In still another example of the present invention, there is provided an aqueous molten hydroxyl polymer composition comprising a fibrous element forming polymer, such as a hydroxylated polymer, and a crosslinking system comprising a crosslinking agent and a crosslinking material. dual use which has both a crosslinking promoting agent function (catalyst) and a fast wetting surfactant function (wetting), for example, an ammonium and / or iminium sulfosuccinate diester salt . In yet another example of the present invention, there is provided a polymeric structure, such as a fibrous element, derived from an aqueous molten hydroxyl polymer composition of the present invention. In yet another example of the present invention there is provided a method of manufacturing a polymeric structure, for example, a fibrous element, of the present invention comprising the steps of: a. providing an aqueous molten hydroxyl polymer composition comprising a fibrous element forming polymer, such as a hydroxylated polymer, and a crosslinking system comprising a crosslinking agent and a dual-use material which has both crosslinking promoting agent (catalyst) and a fast wetting surfactant function (wetting), for example, an ammonium and / or iminium sulfosuccinate diester salt; and B. performing a polymer treatment of the aqueous hydroxyl polymer composition melt such that one or more polymeric structures, for example, fibrous elements, are formed. In yet another example of the present invention there is provided a method of manufacturing a fibrous structure of the present invention, comprising: a. providing an aqueous molten hydroxyl polymer composition comprising a fibrous element forming polymer, such as a hydroxylated polymer, and a crosslinking system comprising a crosslinking agent and a dual-use material which has both a function of crosslinking aiding agent (catalyst) and a fast wetting surfactant function (wetting), for example, an ammonium and / or iminium sulfosuccinate diester salt; and B. performing a polymer treatment of the aqueous hydroxyl polymer composition melt such that a plurality of fibrous elements is formed; vs. collecting the fibrous elements, for example, in a mutually entangled manner, on a collection device such that a fibrous structure is formed. In yet another example of the present invention, there is provided a monolayer or multilayer toilet tissue product comprising a fibrous structure of the present invention. Thus, the present invention relates to polymeric structures, such as fibrous elements, comprising one or more dual-use materials and / or dual-use material components, for example, an ammonium sulfosuccinate diester salt and / or iminium and / or its ions and / or sulfosuccinic acid diester and / or ammonia and / or an amine, an aqueous molten hydroxyl polymer composition comprising a dual-use material which has both a crosslinking promoting agent (catalyst) and a fast wetting surfactant function (wetting), for example, ammonium and / or iminium sulfosuccinate diester salt, polymeric structures, e.g. fibrous materials made from such aqueous hydroxyl polymer melt compositions, fibrous structures made from such fibrous elements, and methods of making the same.
[0014] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of an example of a method of manufacturing a fibrous structure according to the present invention; Fig. 2 is a schematic representation of an example of a part of a method of manufacturing a fibrous structure according to the present invention; Figure 3 is a schematic representation of an example of a meltblown die according to the present invention; Fig. 4A is a schematic representation of an example of a sheath of a twin-screw extruder according to the present invention; Figure 4B is a schematic representation of an example of a screw and mix element configuration of the twin screw extruder of Figure 4A; Figure 5A is a schematic representation of an example of a quill of a twin-screw extruder suitable for use in the present invention; Figure 5B is a schematic representation of an example of a configuration of screw and mixing elements suitable for use in the sleeve of Figure 5A; Figure 6 is a schematic representation of an example of a method for synthesizing a fibrous element according to the present invention; Figure 7 is a schematic representation of a partial side view of the process shown in Figure 6 showing an example of an attenuation zone; Figure 8 is a schematic plan view taken along the lines 8-8 of Figure 7 and showing a possible scheduling of a plurality of extrusion nozzles arranged to provide the fibrous elements of the present invention; and Figure 9 is a view similar to that of Figure 8 and showing a possible arrangement of orifices for providing boundary air around the attenuation zone shown in Figure 7. DETAILED DESCRIPTION OF THE INVENTION Definitions A "polymeric structure" as used herein refers to any physical structure formed as a result of treating an aqueous molten hydroxyl polymer composition of the present invention in such a physical structure. Non-limiting examples of polymeric structures according to the present invention include fibrous elements, films, coatings and / or foams. The polymeric structures of the present invention are naturally occurring non-naturally occurring structures. In other words, they are physical structures made by man. A "fibrous element" as used herein refers to an elongate particulate material having a length that is significantly greater than its average diameter, i.e., a length to average diameter ratio of at least about 10. fibrous element may be a filament or a fiber. In one example, the fibrous element is a single fibrous element rather than a wire comprising a plurality of fibrous elements. The fibrous elements of the present invention can be spun from the molten polymer compositions by appropriate spinning operations, such as by meltblowing and / or direct spinning, and / or they can be obtained from natural sources such as than plant sources, for example, trees.
[0015] The fibrous elements of the present invention may be monocomponent and / or multicomponent. For example, the fibrous elements may comprise bicomponent fibers and / or filaments. The bicomponent fibers and / or filaments may be in any form, such as side-by-side, core and sheath, islets in the sea and the like. "Filament" as used herein means an elongated particulate material as hereinbefore described having a length greater than or equal to 5.08 cm (2 inches) and / or greater than or equal to 7.62 cm (3 inches) and / or greater than or equal to 10.16 cm (4 inches) and / or greater than or equal to 15.24 cm (6 inches). Filaments are typically considered continuous or essentially continuous in nature. The filaments are relatively longer than the fibers. Non-limiting examples of filaments include meltblown and / or spunbonded filaments. Non-limiting examples of polymers that can be spun into filaments include natural polymers, such as starch, starch derivatives, cellulose, such as rayon and / or lyocell, and cellulose derivatives. hemicellulose, hemicellulose derivatives, and synthetic polymers, including, but not limited to, polyvinyl alcohol, thermoplastic polymers, such as polyesters, nylons, polyolefins such as polypropylene, polyethylene filaments, and biodegradable thermoplastic fibers such as polylactic acid filaments, polyhydroxyalkanoate filaments, polyesteramide filaments and polycaprolactone filaments. "Fiber" as used herein means an elongated particulate material as previously described which is less than 5.08 cm (2 inches) in length and / or less than 1.5 inches (3.8 cm) and / or less than 2.54 cm (1 in). Fibers are typically considered discontinuous by nature. Non-limiting examples of fibers include pulp fibers, such as wood pulp fibers, and staple synthetic fibers such as polypropylene, polyethylene, polyester, copolymer, rayon, glass fibers. and polyvinyl alcohol fibers. The staple fibers may be produced by spinning a tow of filaments and then cutting the tow into segments of less than 5.08 cm (2 inches), thereby producing the fibers. In one example of the present invention, a fiber may be a naturally occurring fiber, which means that it is obtained from a naturally occurring source, such as a vegetative source, by for example, a tree and / or a plant, such as trichomes. These fibers are generally used in papermaking and are often referred to as papermaking fibers. Paper making fibers useful in the present invention include cellulosic fibers commonly known as wood pulp fibers. Applicable wood pulps include chemical pulps, such as Kraft, sulfite, and sulfate pulps, as well as mechanical pulps including, for example, wood pulp, thermomechanical pulp, and chemically modified thermomechanical pulp. Chemical pulps, however, may be preferred because they provide a softer feel to the fibrous structures made therefrom. Pulps derived from both deciduous trees (hereinafter also referred to as "hardwoods") and coniferous trees (hereinafter also referred to as "coniferous woods") may be used. The hardwood and coniferous wood fibers may be mixed, or alternatively may be layered to provide a laminated web. Fibers derived from recycled paper, which may contain all or some of the aforementioned fiber categories as well as other non-fibrous polymers such as fillers, softening agents, dry and wet strength improvers and adhesives, used to facilitate the manufacture of the original paper, can also be applied to the present invention.
[0016] In addition to the various wood pulp fibers, other cellulosic fibers such as cotton linters, rayon, lyocell and bagasse fibers may be used in the fibrous structures of the present invention. "Fibrous structure" as used herein means a structure that includes one or more fibrous elements. In one example, a fibrous structure according to the present invention refers to an association of fibrous elements that together form a structure capable of performing a function. In another example of the present invention, a fibrous structure comprises a plurality of mutually entangled fibrous elements, e.g., filaments. "Toilet paper product" as used herein means a relatively low density flexible fibrous structure useful as a wiping means for cleaning after urinating or defecating (toilet paper) for otorhinolaryngological discharge (handkerchiefs). ), absorbent and multipurpose cleaning uses (absorbent towels) and wipes such as wet and dry wipes. The sanitary tissue product may be convoltively wound on itself around a core or without a core to form a toilet paper roll or may be in the form of separate sheets. In one example, the sanitary tissue product of the present invention comprises one or more fibrous structures according to the present invention.
[0017] The sanitary tissue products and / or fibrous structures of the present invention may have a basis weight of from about 1 g / m 2 to about 5,000 g / m 2 and / or from about 10 g / m 2 to about 500 g / m 2 and or from about 10 g / m 2 to about 300 g / m 2 and / or from about 10 g / m 2 to about 120 g / m 2 and / or from about 15 g / m 2 to about 110 g / m 2 and / or from about 20 g / m 2 to about 100 g / m 2 and / or from about 30 to 90 g / m 2 as determined by the surface mass test method described herein. In addition, the sanitary tissue product of the present invention may have a basis weight of between about 40 g / m 2 and about 120 g / m 2 and / or between about 50 g / m 2 and about 110 g / m 2 and / or about 55 g / m 2 and about 105 g / m 2 and / or between about 60 g / m 2 and 100 g / m 2, as determined by the surface mass test method described herein.
[0018] The sanitary tissue products of the present invention may have a total dry tensile strength greater than about 0.58 N / cm and / or about 0.76 N / cm to about 3.86 N / cm and or from about 0.96 N / cm to about 3.29 N / cm (about 59 g / cm and / or about 78 g / cm to about 394 g / cm and / or about 98 g / cm at about 335 g / cm). In addition, the sanitary tissue product of the present invention may have a total dry tensile strength greater than about 1.92 N / cm and / or about 1.92 N / cm to about 3.86 N / cm. cm and / or from about 2.17 N / cm to about 3.29 and / or from about 2.31 N / cm to about 3.09 N / cm (about 196 g / cm and / or about 196 g / cm at about 394 g / cm and / or about 216 g / cm to about 335 g / cm and / or about 236 g / cm to about 315 g / cm). In one example, the sanitary tissue product has a total dry tensile strength of less than about 3.86 N / cm and / or less than about 3.29 N / cm (about 394 g / cm and / or less than about about 335 g / cm) as measured by the elongation / tensile strength / total energy absorbed / tangent modulus test method described herein. The sanitary tissue products of the present invention may have a density of less than 0.60 g / cm3 and / or less than 0.30 g / cm3 and / or less than 0.20 g / cm3 and / or less than 0 , 15 g / cm3 and / or less than 0.10 g / cm3 and / or less than 0.07 g / cm3 and / or less than 0.05 g / cm3 and / or about 0.01 g / cm3 at about 0.20 g / cm 3 and / or from about 0.02 g / cm 3 to about 0.15 g / cm 3 and / or from about 0.02 g / cm 3 to about 0.10 g / cm 3 such that measured according to the density test method described herein. The sanitary tissue products of the present invention may be in the form of rolls of sanitary tissue product. Such rolls of sanitary tissue product may comprise a plurality of interconnected, but perforated, sheets of fibrous structure, which are separately distributable from adjacent sheets. The sanitary tissue products of the present invention may include additives such as softening agents, temporary moisture resistance agents, permanent moisture resistance agents, bulk softening agents, lotions, silicones, and the like. wetting agents, latices, structured latices, and other types of additives suitable for inclusion in and / or on sanitary tissue products. "Canvas" as used herein means a material that is used to coat solid additives present on and / or within a nonwoven substrate of the fibrous structures of the present invention, so that solid additives are positioned between the scrim and a layer of the fibrous structure. In one example, the scrim covers the solid additives so that they are positioned between the scrim and a surface of the nonwoven substrate of the fibrous structure. In another example, the scrim is a minor component (e.g., less than 25% of the basis weight) relative to the nonwoven substrate of the basis weight of the fibrous structure.
[0019] "Hydroxylated polymer" as used herein includes any hydroxyl-containing polymer that can be incorporated into a filament of the present invention. In one example, the hydroxylated polymer of the present invention includes more than 10% and / or more than 20% and / or more than 25% by weight of hydroxyl moieties based on the weight of the hydroxylated polymer. In another example, the hydroxyl in the hydroxyl-containing polymer is not part of a larger functional group such as a carboxylic acid group. "Non-thermoplastic" as used herein means, with respect to a material, such as a fibrous element as a whole and / or a polymer, such as a cross-linked polymer, within a fibrous element that the fibrous element and / or the polymer have no melting point and / or softening point, which allows them to flow under pressure, in the absence of a plasticizer, such as water, glycerine, sorbitol, urea and the like. "Thermoplastic" as used herein means, with respect to a material such as a fibrous element as a whole and / or a polymer within a fibrous element, that the fibrous element and / or the polymer have a melting point and / or a softening point at a certain temperature, which allows them to flow under pressure. "Cellulose-free" as used herein means less than 5% and / or less than 3% and / or less than 1% and / or less than 0.1% and / or 0% by weight a cellulosic polymer, a cellulose derivative polymer and / or a cellulosic copolymer is present in the fibrous element. In one example, "not containing cellulose" means that less than 5% and / or less than 3% and / or less than 1% and / or less than 0.1% and / or 0% by weight of a Cellulosic polymer is present in the fibrous element. A "dual-use material" as used herein refers to a chemical compound that exhibits both a crosslinking agent function and a fast wetting surfactant function. A non-limiting example of a dual-use material includes ammonium and / or iminium sulfosuccinate diester salts. A "dual-use material component" as used herein is a chemical entity, such as a compound or an ion, that results from a dual-use material in a processing of a composition aqueous solution of molten hydroxyl polymer comprising the dual-use material. Non-limiting examples of dual-use material components include ammonium and / or iminium sulfosuccinate diester salts and / or their sulfosuccinic acid ions and / or diester and / or ammonia and / or or amines.
[0020] A "crosslinking promoting agent" and / or "crosslinking promoting agent function" as used herein refers to any material that is capable of activating a crosslinking agent, thereby transforming the agent. from cross-linking from its non-activated state to its activated state. In other words, when a crosslinking agent is in its non-activated state, the hydroxylated polymer present in the molten hydroxylated aqueous polymer composition does not undergo unacceptable crosslinking. Unacceptable crosslinking causes the shear viscosity and the n-value to fall outside the specified ranges which are determined by the shear viscosity of the test method for measuring an aqueous hydroxyl polymer composition melted, described herein. In the case of imidazolidinone crosslinking agents, the pH and temperature of the molten hydroxylated aqueous polymer composition should be in the desired pH of from about 4.5 to about 8 as measured by the pH test method. aqueous composition of molten hydroxyl polymer described herein; unacceptable crosslinking occurs outside these ranges. The terms "fast wetting surfactant" and / or "fast wetting surfactant component" and / or "fast wetting surfactant function" as used herein refer to a surfactant and / or a surfactant component. , such as an ion from a fast wetting surfactant, for example, a sulfosuccinate diester ion (anion), which has a critical micelle concentration (CMC) greater than 0.15% by weight and / or d at least 0.25% and / or at least 0.50% and / or at least 0.75% and / or at least 1.0% and / or at least 1%, 25% and / or at least 1.4% and / or less than 10.0% and / or less than 7.0% and / or less than 4.0% and / or less than 3.0% and or less than 2.0% by weight. An "aqueous molten hydroxyl polymer composition" or "molten polysaccharide aqueous composition" as used herein refers to a composition comprising water and a melt-treated polymer, such as an element-forming polymer. melt-processed fibrous material, for example, a melt-treated hydroxyl polymer, such as a melt-treated polysaccharide. "Fusion-treated fibrous element forming polymer" as used herein means any polymer which, by the effect of elevated temperatures, pressure and / or external plasticizers, can be softened to such a degree that it can be brought to a fluid state, and in this condition, can be shaped as desired. "Melt-Processed Hydroxylated Polymer" as used herein means any polymer containing more than 10% and / or more than 20% and / or more than 25% by weight of hydroxyl groups by weight of the polymer and which has been melt treated, with or without the aid of an external plasticizer. More generally, the melt-treated hydroxyl polymers include polymers which, by the effect of high temperatures, pressure and / or external plasticizers, can be softened to such a degree that they can be brought to a fluid state. , and in this condition, can be shaped as desired. A "mixture" as used herein means that two or more materials, such as a fibrous element-forming polymer, for example, a hydroxylated polymer, and a salt and / or sulfosuccinate diester acid Ammonium are in contact with each other, as homogeneously or homogeneously mixed together, within a filament. In other words, a filament formed from a material but having an outer covering of another material is not a mixture of materials for purposes of this invention. However, a fibrous element formed from two different materials is a mixture of materials for purposes of the present invention, even though the fibrous element further comprises an outer coating of a material. "Copolymer" as used herein refers to a polymer comprising two or more different monomeric units. In other words, the copolymer is derived from two or more different monomers. For example, the copolymer may comprise two different monomer units. In another example, the copolymer may comprise three different monomeric units (terpolymer). In yet another example, the copolymer may comprise more than three different monomeric units. The monomeric units can be introduced into the polymerization in any order. The copolymer of the present invention may be produced by any suitable polymerization process, for example, radical polymerization, for example random random polymerization and / or active free radical polymerization. The polymerization can be random or controlled by several means, including, but not limited to, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT). In one example, the polymerization is an emulsion polymerization. "Associate", "associate", "association", and / or "associating", as used herein with respect to fibrous elements, means combining, in direct contact or indirect contact, fibrous elements of a kind a fibrous structure is formed. In one example, the associated fibrous elements may be bonded together, for example, by adhesives and / or thermal bonds. In another example, the fibrous elements may be associated with each other by being deposited on the same fibrous structure manufacturing belt. "Average diameter" as used herein, relative to a fibrous element, is measured according to the average diameter test method described herein. In one example, a fibrous element of the present invention has a mean diameter less than 50 μm and / or less than 25 μm and / or less than 20 μm and / or less than 15 μm and / or less than 10 μm and / or less than 6 μm and / or greater than 1 μm and / or greater than 3 μm. "Weight per unit area" as used herein is the weight per unit area of a sample, indicated in pounds / 3000 sq. Ft. Or g / m 2, as determined by the surface mass test method described. right here. "Machine direction" or "MS" as used herein refers to the direction parallel to the flow of the fibrous structure through the fibrous structure manufacturing machine and / or the manufacturing equipment of the fibrous structure. toilet paper. Typically, the SM is substantially perpendicular to the perforations present in the fibrous structure. The "cross-machine direction" or "ST" as used herein refers to the direction perpendicular to the machine direction in the same plane as the fibrous structure and / or that the sanitary tissue product comprising the fibrous structure. "Layer" or "layers" as used herein means an individual fibrous structure or fibrous structure sheet, optionally to be disposed in face-to-face relationship substantially contiguous with other layers, forming a multi-layered fibrous structure It is also contemplated that a single fibrous structure can effectively form two "layers" or "layers", for example, by being folded on itself. As used herein, the articles "a" and "an" when used herein, for example, "anionic surfactant" or "a fiber" are intended to refer to one or more of the material which is described. All percentages and ratios are by weight unless otherwise indicated. All percentages and ratios are calculated on the basis of total composition unless otherwise indicated. Unless otherwise indicated, all levels of constituent or composition are referred to the level of that component or composition, and exclude impurities, for example, residual solvents or by-products, which may be present in sources available in trade. Polymeric Structures - Fibrous Elements The polymeric structures, for example, the fibrous elements, of the present invention comprise a fibrous element-forming polymer, such as a hydroxylated polymer, for example, a cross-linked hydroxy-polymer, and a dual-material. use and / or a dual-purpose material component. In one example, the fibrous elements may comprise two or more fibrous element-forming polymers, such as two or more hydroxylated polymers. In another example, the fibrous elements may comprise two dual-use materials and / or dual-use material components or more. In another example, the fibrous element may comprise two or more fibrous element-forming polymers, such as two or more hydroxylated polymers, at least one of which is starch and / or a starch derivative, and one of which is a non-starch and / or non-starch derivative, such as polyvinyl alcohol. In yet another example, the fibrous elements of the present invention may comprise two or more fibrous element-forming polymers of which at least one is a hydroxylated polymer and at least one of which is a non-hydroxylated polymer. In yet another example, the fibrous elements of the present invention may comprise two or more non-hydroxylated polymers. In one example, at least one of the non-hydroxylated polymers has a weight average molecular weight greater than 1,400,000 g / mol and / or is present in the fibrous elements at a concentration greater than its entanglement concentration (Ce) and / or has a polydispersity greater than 1.32. In yet another example, at least one of the non-hydroxylated polymers comprises an acrylamide-based copolymer. In one example, the fibrous element comprises a filament. In another example, the fibrous element comprises a fiber, such as a filament that has been cut into fibers. In one example, the polymeric structure, for example, a fibrous element, such as a filament, of the present invention has a conductivity less than 110 and / or less than 100 and / or less than 90 and / or less than 85 and / or up to about 0 and / or up to about 5 and / or up to about 10 microsiemens as measured according to the conductivity test method described herein.
[0021] Fibrous Element-forming Polymers The aqueous hydroxyl-melt polymer compositions of the present invention and / or the polymeric structures, for example, fibrous elements, such as filaments and / or fibers, of the present invention that associate with each other. for forming the fibrous structures of the present invention, contain at least one fibrous element-forming polymer, such as a hydroxylated polymer, and may contain other types of polymers such as non-hydroxylated polymers, which have molecular weights weight averages greater than 500,000 g / mol, and mixtures thereof as determined by the weight average molecular weight method described herein. Non-limiting examples of hydroxylated polymers according to the present invention include polyols, such as polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch, starch derivatives, copolymers of starch, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives such as cellulose ether and ester derivatives, cellulose copolymers, hemicellulose, hemicellulose derivatives, copolymers of hemicellulose, gums, arabinans, galactans, proteins and various other polysaccharides and mixtures thereof. In one example, a hydroxylated polymer of the present invention comprises a polysaccharide. In another example, a hydroxylated polymer of the present invention comprises a non-thermoplastic polymer. The hydroxylated polymer may have a weight average molecular weight of from about 10,000 g / mol to about 40,000,000 g / mol and / or greater than 100,000 g / mol and / or greater than 1,000,000 g / mol and / or greater than 3,000,000 g / mol and / or greater than 3,000,000 g / mol to about 40,000,000 g / mol, as determined by the weight average molecular weight method described herein. The higher and lower molecular weight hydroxyl polymers can be used in combination with hydroxylated polymers having a desired weight average molecular weight. The polyvinyl alcohols herein may be grafted to other monomers to modify its properties. A wide range of monomers has been successfully grafted to polyvinyl alcohol. Non-limiting examples of such monomers include vinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethyl methacrylate, acrylonitrile, 1,3-butadiene, methyl methacrylate, methacrylate and the like. methacrylic acid, vinylidene chloride, vinyl chloride, vinylamine and a variety of acrylate esters. Polyvinyl alcohols include the various hydrolysis products formed from polyvinyl acetate. In one example, the degree of hydrolysis of the polyvinyl alcohols is greater than 70% and / or greater than 88% and / or greater than 95% and / or about 99%. "Polysaccharides" as used herein refers to polysaccharides and natural polysaccharide derivatives and / or modified polysaccharides. Suitable polysaccharides include, but are not limited to, starches, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives, copolymers cellulose, hemicellulose, hemicellulose derivatives, hemicellulose copolymers, gums, arabinans, galactans and mixtures thereof. The polysaccharide may have a weight average molecular weight of from about 10,000 to about 40,000,000 g / mol and / or greater than about 100,000 and / or greater than about 1,000,000 and / or greater than about 3,000,000 and or greater than about 3,000,000 to about 40,000,000, as determined by the weight average molecular weight method described herein. The polysaccharides of the present invention may comprise non-cellulosic hydroxyl polymers and / or based on non-cellulosic derivatives and / or based on non-cellulosic copolymers. A non-limiting example of such non-cellulosic polysaccharides may be selected from the group consisting of: starches, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, hemicellulose, hemicellulose derivatives, hemicellulose copolymers and mixtures thereof.
[0022] In one example, the hydroxylated polymer comprises starch, a starch derivative and / or a starch copolymer. In another example, the hydroxylated polymer comprises starch and / or a starch derivative. In yet another example, the hydroxylated polymer comprises starch. In one example, the hydroxylated polymer comprises ethoxylated starch. In another example, the hydroxylated polymer comprises starch diluted with acid. In yet another example, the hydroxylated polymer comprises dent corn starch. As is known, a natural starch can be chemically or enzymatically modified, as is well known in the art. For example, natural starch can be diluted with acid, hydroxyethyl, hydroxypropyl, etheruccinylated or oxidized. In one example, the starch comprises a high amylopectin natural starch (a starch that contains more than 75% and / or more than 90% and / or more than 98% and / or about 99% by weight of amylopectin relative to the total weight of the starch). These natural starches with high amylopectin content can come from agricultural sources, which have the advantage of being plentiful, easy to renew and relatively inexpensive. Chemical modifications of the starch usually include acid or alkaline catalyzed hydrolysis and chain cleavage (by oxidation and / or enzymatic) to reduce molecular weight and molecular weight distribution. Suitable compounds for chemical modification of starch include organic acids such as citric acid, acetic acid, glycolic acid, and adipic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and partial salts of polycarboxylic acids, for example, KH 2 PO 4, NaHSO 4; Group la or Ha metal hydroxides, such as sodium hydroxide and potassium hydroxide; ammonia; oxidizing agents such as hydrogen peroxide, benzoyl peroxide, ammonium persulfate, potassium permanganate, hypochlorous salts, and the like; and their mixtures. "Modified starch" is a starch that has been chemically or enzymatically modified. The modified starch is different from a native starch, which is a starch which has not been modified, chemically or otherwise, in any way. The chemical modifications may also include derivatization of the starch by reaction of its hydroxyl groups with alkylene oxides, and other ether, ester, urethane, carbamate, or isocyanate. Hydroxyalkyl, ethersuccinylated, acetylated or carbamate starches or mixtures thereof may be used as chemically modified starches. The degree of substitution of the chemically modified starch ranges from 0.001 to 3.0, and more precisely from 0.003 to 0.2. Biological modifications of starch can include bacterial digestion of carbohydrate linkages, or enzymatic hydrolysis using enzymes such as amylase, amylopectase, and the like. Generally, all types of natural starches can be used in the present invention. Naturally suitable starches present may include, but are not limited to: corn starch, potato starch, sweet potato starch, wheat starch, sago starch, soybean starch tapioca starch, rice starch, soy starch, arrowroot starch, amioca starch, fern starch, lotus starch, waxy corn starch and corn starch rich in amylose. Naturally occurring starches, particularly corn starch and wheat starch, can be particularly advantageous because of their low cost and availability.
[0023] In one example, to generate rheological properties suitable for high-speed fibrous element spinning processes, the molecular weight of the unmodified natural starch can be reduced. The optimum molecular weight depends on the type of starch used. For example, a starch with a low level of amylose component, such as a waxy maize starch, disperses rather easily in an aqueous solution with the application of heat and does not degrade or recrystallize significantly. With these properties, a waxy maize starch can be used at a weight average molecular weight, for example, in the range of 500,000 g / mol to 40,000,000 g / mol, as determined by the weight average molecular weight described herein. Modified starches such as hydroxyethyl dent corn starch, which contains about 25% amylose, or oxidized dent corn starch, tend to downgrade more than waxy maize starch, but less than starch diluted with acid. This retrogradation, or recrystallization, acts as a physical crosslinking to effectively increase the weight average molecular weight of the starch in an aqueous solution. Therefore, an appropriate weight average molecular weight for a typical hydroxyethyl dent corn starch commercially available with 2% by weight of hydroxyethylation or an oxidized dent corn starch is from about 200,000 g / mol to about 10,000. 000 g / mol. For ethoxylated starches having higher levels of ethoxylation, for example, hydroxyethylated corn corn starch with 5% by weight hydroxyethylation, weight average molecular weights of up to 40,000,000 g / mol, such as determined by the weight average molecular weight test method described herein, may be suitable for the present invention. For acid-diluted tooth corn starch, which tends to degrade more than oxidized tooth corn starch, the weight average molecular weight ranges from about 100,000 g / mol to about 15,000,000 g / mol. g / mol, as determined by the weight average molecular weight method described herein. The weight average molecular weight of the starch may also be reduced to a range desirable for the present invention by physical / mechanical degradation (eg, by the supply of thermomechanical energy from the process equipment).
[0024] The natural starch can be hydrolysed in the presence of an acid catalyst to reduce the molecular weight and molecular weight distribution of the composition. The acid catalyst may be selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, ammonium chloride and any combination thereof. In addition, a chain-splitting agent may be incorporated in a spinnable starch composition such that the chain scission reaction takes place substantially at the same time as mixing the starch with other components. Non-limiting examples of oxidative chain scavengers useful herein include ammonium persulfate, hydrogen peroxide, hypochlorite salts, potassium permanganate, and mixtures thereof. Typically, the chain scavenger is added in an amount effective to lower the weight average molecular weight of the starch to the desirable range. It is found that compositions having modified starches in the appropriate weight average molecular weight ranges have appropriate shear viscosities, and thus improve the processability of the composition. Improved processability is evident in fewer process interruptions (for example, fewer breaks, tests, defects, interruptions) and improved surface appearance and strength properties of the final product , such as the fibers of the present invention. In one example, the fibrous element of the present invention is free of water insoluble thermoplastic polymers. In one example, the fibrous element-forming polymers may be present in the molten hydroxylated aqueous polymer composition in an amount of from about 20% to about 50% and / or from about 30% to about 50% and or from about 35% to about 48% by weight of the aqueous composition of molten hydroxyl polymer and present in a polymeric structure, for example, a fibrous element and / or a fibrous structure, at a rate of about 50% at about 100% and / or from about 60% to about 98% and / or from about 75% to about 95% by weight of the polymeric structure, for example, a fibrous element and / or a fibrous structure. Other Polymers The aqueous hydroxyl polymer compositions of the present invention and / or the polymeric structures, for example, fibrous elements, such as filaments of the present invention, may comprise, in addition to the fibrous element forming polymer. other polymers, such as non-hydroxylated polymers. Non-limiting examples of suitable non-hydroxylated polymers that may be included in the fibrous elements of the present invention include non-hydroxylated polymers having a weight average molecular weight greater than 500,000 g / mol and / or greater than 750,000 g. and / or more than 1 000 000 g / mol and / or more than 1 250 000 g / mol and / or more than 1 400 000 g / mol and / or at least 1 450 000 g / mol and / or at least 1 500 000 g / mol and / or less than 10 000 000 g / mol and / or less than 5 000 000 g / mol and / or less than 2 500 000 g / mol and / or less than 10 000 000 g / mol and / or less 2,000,000 g / mol and / or less than 1,750,000 g / mol as determined by the weight average molecular weight method described herein. In one example, the non-hydroxylated polymer has a polydispersity greater than 1.10 and / or at least 1.20 and / or at least 1.30 and / or at least 1.32 and / or at least 1.40 and / or at least 1.45. Non-limiting examples of suitable non-hydroxylated polymers include polyacrylamide polymers and derivatives such as carboxyl-modified polyacrylamide polymers and copolymers, including polyacrylic acid, poly (hydroxyethyl) acrylic acid, methacrylic acid and their partial esters; vinyl polymers, especially polyvinyl alcohol, polyvinylpyrrolidone and the like; polyamides; polyalkylene oxides such as polyethylene oxide and mixtures thereof. Graft copolymers or copolymers made from monomer mixtures selected from the abovementioned polymers are also suitable herein. Non-limiting examples of commercially available polyacrylamides include nonionic polyacrylamides such as Kemira N300 or Hyperfloc® NF221, NF301, and NF241 from Hychem, Inc. In one example, non-hydroxylated polymers may be present in from about 0.01% to about 10% and / or from about 0.05% to about 5% and / or from about 0.075% to about 2.5% and / or about 0.1% % to about 1% by weight of the aqueous composition of molten hydroxyl polymer, filament and / or fibrous structure. In yet another example, the non-hydroxylated polymer comprises a linear polymer. In another example, the non-hydroxylated polymer comprises a long-chain branched polymer. In yet another example, the non-hydroxylated polymer is compatible with the hydroxylated polymer at a concentration greater than the entangling concentration Ce of the non-hydroxylated polymer. Non-limiting examples of suitable non-hydroxylated polymers are selected from the group consisting of: polyacrylamide and its derivatives; polyacrylic acid, polymethacrylic acid and their esters; polyethylene imine; copolymers made from mixtures of the aforementioned polymers; and their mixtures. In one example, the non-hydroxylated polymer comprises a polyacrylamide. In one example, the fibrous element comprises two or more non-hydroxylated polymers, such as two or more polyacrylamides, such as two or more polyacrylamides of different weight average molecular weight. In one example, the non-hydroxylated polymer comprises a copolymer based on acrylamide. In another example, the non-hydroxylated polymer comprises a polyacrylamide and acrylamide-based copolymer. In one example, the acrylamide-based copolymer is derived from an acrylamide monomer and at least one monomer selected from the group consisting of: grafted hydroxyl-containing monomers, monomers containing a grafted hydroxyalkyl ether, monomers containing a grafted alkylated hydroxy-ester, monomers containing a grafted hydroxyl alkylamide, and mixtures thereof. In one example, the acrylamide-based copolymer comprises an acrylamide monomer unit and at least one monomeric unit selected from the group consisting of: grafted hydroxyl-containing monomeric units, monomeric units containing a grafted alkyl-alkylether, monomeric units containing a hydroxyl-alkyl ester grafted, monomeric units containing a grafted hydroxyl alkylamide, and mixtures thereof. Crosslinking System A crosslinking system comprising a crosslinking agent capable of crosslinking a hydroxylated polymer in an aqueous composition of molten hydroxyl polymer, such as an imidazolidinone crosslinking agent, and a dual-use material which exhibits both a function of a crosslinking promoting agent and a fast wetting surfactant function, for example an ammonium and / or iminium sulfosuccinate diester salt, are present in the aqueous hydroxylated polymer composition and / or are added to the aqueous molten hydroxyl polymer composition prior to the polymeric treatment of the molten hydroxylated aqueous polymer composition and / or the crosslinking agent and / or the dual-use material (s) and / or the ) component (s) of dual-use material, for example an ammonium and / or iminium sulfosuccinate diester salt, may be present in the polymeric structures, e.g. e, fibrous elements, produced from the aqueous molten hydroxyl polymer compositions of the present invention. In general, any aqueous crosslinking system that benefits from a thermally triggered latent acid catalyst can be envisioned for the use of a dual-purpose material, for example, an ammonium sulfosuccinate diester salt and or iminium which accelerates the removal of water and forms an acid (its sulfosuccinic acid diester) during curing (for example, during heating). Examples of crosslinking systems that could utilize a dual-use material of the present invention, for example, an ammonium and / or iminium sulfosuccinate diester salt, include, in addition to dihydroxy-ethylene-urea, various amino resins, for example, melamine-formaldehyde, urea-formaldehyde, benzoguanamine-formaldehyde, glycolurilformaldehyde and methacrylamide-formaldehyde combined with hydroxyl-functional acrylics and polyesters.
[0025] During the crosslinking of the hydroxylated polymer during the curing step, the crosslinking agent becomes an integral part of the polymer structure due to the crosslinking of the hydroxylated polymer, as shown in the following schematic representation: Hydroxylated polymer - Crosslinking agent - Hydroxylated Polymer In addition, crosslinking aids which are not the dual-use materials of the present invention, for example, ammonium and / or iminium sulfosuccinate diester salts, may be present as sub-products. -products of synthesis of dual-use materials. For example, in the synthesis of maleic diester, synthetic precursor to ammonium sulfosuccinic ester salt, an acid catalyst such as toluenesulfonic acid is used in the esterification process. In the next step of the synthesis of the ammonium sulfosuccinic ester salt, ammonium bisulfite is reacted with the double bond. The ammonium bisulfite will also neutralize the toluenesulfonic acid used in the esterification to give the ammonium salt of toluenesulfonic acid which may advantageously remain in the ammonium sulfosuccinic ester salt preparation. In one example of the present invention, a crosslinking system comprising a crosslinking agent capable of crosslinking a fibrous element forming polymer, for example a hydroxylated polymer, and a dual-use material of the present invention are present in a crosslinking system. aqueous composition of molten hydroxyl polymer of the present invention. The melt processing of the molten hydroxylated aqueous polymer composition, for example, the polymeric treatment of the aqueous hydroxyl polymer composition melted into fibrous elements, and then subjecting the fibrous elements to a hardening step causes crosslinking of the hydroxylated polymer producing a crosslinked hydroxylated polymer, for example, a cross-linked polysaccharide, such as a crosslinked starch. The crosslinking agent and / or the dual-use material may be added to the molten hydroxylated aqueous polymer composition, for example, prior to the polymer treatment of the aqueous molten hydroxyl polymer composition. The crosslinking agent and / or the dual-use material and / or the dual-use material component (s) may be present in the fibrous elements produced from the aqueous molten hydroxyl polymer compositions of the present invention. . In one example, the crosslinking agent may be present in the molten hydroxylated aqueous polymer composition at a level of from about 0.25% to about 6% and / or from about 0.5% to about 5% and or from about 0.5% to about 4% by weight of the aqueous hydroxyl polymer composition and present in a polymeric structure, for example, a fibrous element and / or a fibrous structure, at a rate of about 0 From about 5% to about 10% and / or from about 0.5% to about 8% and / or from about 1% to about 7% by weight of the polymeric structure, for example, a fibrous element and / or fibrous structure. Dual-Purpose Material / Dual-Purpose Material Component Non-limiting examples of suitable dual-use materials include ammonium and / or iminium sulfosuccinate diester salts and / or sulfosuccinate diester salt derivatives. ammonium and / or iminium. A function of the dual-use material, the crosslinking promoting agent function, serves to activate a crosslinking agent present within an aqueous molten hydroxyl polymer composition of the present invention under activation conditions, thereby transforming the crosslinking agent. makes the crosslinking agent from its inactivated state to its activated state so that the crosslinking agent crosslinks the hydroxylated polymer (s) within the molten hydroxylated aqueous polymer composition.
[0026] In other words, when a crosslinking agent is in its inactivated state, the hydroxylated polymer present in the molten hydroxylated aqueous polymer composition does not undergo unacceptable crosslinking, for example, does not crosslink before being melt processed, for example for example, spun into a polymeric structure, such as a fibrous element.
[0027] The dual-use materials of the present invention comprise one or more ammonium and / or iminium sulfosuccinate diester salts and / or their equivalent sulfosuccinic acid diesters which may exist after transformation / activation of the crosslinking. For example, a crosslinking agent salt, such as an ammonium sulfosuccinate diester salt, is chemically changed to its sulfosuccinic acid diester form and vice versa. Non-limiting examples of ammonium sulfosuccinate diester salts suitable for use as a dual-use material in the present invention include the ammonium salts of the following diesters: bis (bis-isobutyl ester) sulfosuccinic acid, bis ( pentyl ester), sulfosuccinic acid bis (1,3-dimethylbutyl ester), and sulfosuccinic acid bis (2-ethylhexyl ester). In one example, the polymeric structures, for example, fibrous elements, comprise one or more dual-use materials, such as an ammonium and / or iminium sulfosuccinate diester salt and / or its acid diester. sulfosuccinic.
[0028] The ammonium and / or iminium sulfosuccinate diester salts of the present invention may have the following formula (I) shown below. Where MO3S is W and -03S, where W is an ammonium or iminium ion (cation), for example, ± N} I.R24, where n is 1 to 4 and / or 1 to 3 and / or 1 to 2 and / or is 1; and R2 is independently selected from the group consisting of: alkyl, hydroxyalkyl, alkanolamine, aryl, hydroxylaryl or a portion of a heterocyclic ring, for example, an aliphatic or aromatic N-heterocycle; and wherein R is straight or branched C1 to C18 alkyl and / or C1 to C12 linear or branched alkyl and / or linear or branched C1 to C8 alkyl. In one example, the ammonium and / or iminium sulfosuccinate diester salt is made by reacting a sulfosuccinic acid diester and an amine as shown below in Formula II. ## STR3 ## wherein Ak is linear or branched C1 to C18 alkyl and / or linear or branched C1 to C12 alkyl and / or linear or branched C1 to C8 alkyl; and R is H, alkyl, hydroxyalkyl, alkanolamine or a part of a heterocyclic ring, for example an aliphatic or aromatic N-heterocycle.
[0029] The sulfosuccinic acid diester and the amine are both dual-use material components which are formed from the dual-use material in the treatment of an aqueous hydroxyl polymer composition melted into the water. a polymeric structure, for example, a fibrous element, such as a filament, during curing of the polymeric structure.
[0030] Non-limiting examples of suitable alkyl (Ak) groups are selected from the group consisting of: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, 2-ethylhexyl, octyl, decyl, 2-propylheptyl and dodecyl. Non-limiting examples of the amine (N (R 2) 3) from which ammonium and / or iminium are derived are ammonia, dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, 2-amino-2-methyl 1-propanol, 1-methyldiethanolamine, 4-ethylmorpholine, 4-methylmorpholine, 4,4-dimethyloxazolidine. In one example, the amine has a boiling point of less than about 270 ° C. Non-limiting examples of suitable dual-use materials are selected from the group consisting of: sulfosuccinic acid bis (isobutyl ester) ammonium salt; ammonium salt of sulfosuccinic acid bis (pentyl ester); sulphosuccinic acid bis (2-ethylhexyl ester) ammonium salt wherein the ammonium cation is derived from ammonia, dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, 2-amino-2-methyl-1-propanol, methyldiethanolamine, 4-ethylmorpholine, 4-methylmorpholine, 4,4-dimethyloxazolidine.
[0031] The dual-use material may be present in the polymeric structure, such as a fibrous element, for example a filament, at a level of from about 0.1% to 5% and / or about 0.15% at about 4% and / or from about 0.2% to about 2% by weight of the polymeric structure, for example, a fibrous element, such as a filament.
[0032] Another function that is presented by the dual-use material and / or one or more dual-use material components is the fast wetting surfactant function. For example, the dual-use material and / or a dual-use material component of the present invention may have a minimum surface tension in distilled water of less than 34.0 and / or less than 33.0 and / or less at 32.0 and / or less than 31.0 and / or less than 30.0 and / or less than 29.0 and / or less than 28.0 and / or less than 27.0 and / or less than 26 , 75 and / or less than 26.5 and / or less than 26.2 and / or less than 25.0 mN / m and / or more than 0 and / or more than 1.0 mN / m. In yet another example, the dual-use material and / or one or more dual-use material components of the present invention have a critical micelle concentration (CMC) greater than 0.15% and / or at least 0, 25% and / or at least 0,50% and / or at least 0,75% and / or at least 1,0% and / or at least 1,25% and / or at least 1,4% and / or less than 10.0% and / or less than 7.0% and / or less than 4.0% and / or less than 3.0% and / or less than 2.0% by weight and a minimum surface tension in distilled water less than 34.0 and / or less than 33.0 and / or less than 32.0 and / or less than 31.0 and / or less than 30.0 and / or less than 29.0 and / or less than 28,0 and / or less than 27,0 and / or less than 26,75 and / or less than 26,5 and / or less than 26,2 and / or less than 25,0 mN / m and / or the dual-use material and / or one or more dual-use material components of the present invention. have a CMC of at least 1.0% and / or at least 1.25% and / or at least 1.4% and / or less than 4.0% and / or less than 3.0% and / or less than 2.0% by weight and a minimum surface tension in distilled water of less than 34,0 and / or less than 33,0 and / or less than 32,0 and / or less than 31,0 and / or less than 30,0 and / or less than 29,0 and / or less than 28,0 and / or less than 27,0 and / or less than 26,75 and / or less than 26,5 and / or less than 26.2 and / or less than 25.0 mN / m and / or up to more than 0 and / or more than 1.0 mN / m. The CMC and minimum surface tension values in the distilled water of the surfactants can be measured by any suitable methods known in the art, for example, the methods described in Principles of Colloid and Surface Chemistry, pp. 370 to 375. .
[0033] Additional Crosslinking Facilitators In addition to the dual-use material, for example, ammonium and / or iminium sulfosuccinate diester salts, other crosslinking facilitating agents that are not the dual-use material may be present in the molten hydroxylated aqueous polymer composition and / or the polymeric structure, for example, a fibrous element, formed from the molten hydroxylated aqueous polymer composition. Non-limiting examples of such other crosslinking agents which are not the dual-use material include ammonium salts of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropylsulfonic acid, acid, and the like. butanesulfonic acid, isobutylsulfonic acid, sec-butylsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, coumenesulfonic acid, alkylbenzenesulphonic acid, alkylnaphthalenesulphonic acid. Other examples of ammonium salts which are not the dual-use material include ammonium salts from the following amines: dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, 2-amino-2-methyl-1-propanol, methyldiethanolamine, 4-ethylmorpholine, 4-methylmorpholine, 4,4-dimethyloxazolidine. In one example, this amine from which the ammonium salt which is not the dual-use material is produced has a boiling point of less than about 270 ° C. In another example, the dual-use material, for example an ammonium sulfosuccinate diester salt, may be present in the aqueous hydroxyl polymer melt composition and / or the polymeric structure, for example, a fibrous element, formed from the molten hydroxylated aqueous polymer composition, with one or more crosslinking agents that are not the dual-use material, for example, ammonium xylenesulfonate and / or ammonium toluenesulfonate. However, in one example, to minimize the level of salts in the aqueous composition of molten hydroxyl polymer and / or the polymeric structure, for example, a fibrous element, formed from the aqueous molten hydroxyl polymer composition of the present invention, crosslinking agents which are not the additional dual-use material, such as ammonium salts which are not the dual-use material, are minimized if they are non-existent. However, in another example, to minimize the level of cosmotropic salts in the aqueous composition of molten hydroxyl polymer and / or the polymeric structure, for example, a fibrous element, formed from the molten hydroxylated aqueous polymer composition of the present invention. In the present invention, the cosmotropic crosslinking facilitating agents that are not the additional dual-use material, such as the cosmotropic ammonium salts that are not the dual-use material, are minimized if they are non-existent. Non-cosmotropic salts such as ammonium salts of benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, coumenesulfonic acid, alkylbenzenesulfonic acids, and alkylnaphthalenesulfonic acids should not be minimized. When present, crosslinking agents which are not the dual-use material are present in the polymeric structure, for example, a fibrous element, such as a filament, at a rate of from about 0% to 5% and / or from about 0% to about 4% and / or from about 0% to about 2% and / or from about 0% to about 1% and / or from about 0.01% to about 0.75% and / or from about 0.025% to about 0.5% by weight of the polymeric structure, for example, a fibrous element, such as a filament.
[0034] In one example, polymeric structures, for example, fibrous elements, such as filaments, and / or aqueous hydroxyl polymer compositions are free or substantially free (less than 0.025% by weight based on the weight of the polymeric structure and / or the aqueous hydroxyl polymer composition (molten) of cosmotropic salts, such as ammonium sulfate and ammonium citrate. The inclusion of 0.025% and more of a cosmotropic salt, such as ammonium sulfate, even when a salt and / or ammonium alkysulfonate acid is present, can negatively impact properties, such as resistance (eg for example, the total energy absorbed), filaments. However, the inclusion of an amount of an ammonium salt, such as ammonium chloride, for example, an amount which does not produce negative corrosive effects in the processing and spinning equipment, combination with an ammonium alkylsulfonate salt may be present. Tinting Agents The aqueous hydroxyl polymer and / or filament compositions of the present invention may comprise one or more tinting agents. In one example, the total level of one or more tinting agents present within one or more, for example, a plurality, of fibrous elements of a fibrous structure of the present invention is less than 1% and / or less to 0.5% and / or less than 0.05% and / or less than 0.005% and / or greater than 0.00001% and / or greater than 0.0001% and / or greater than 0.001% by weight of the dry fibrous element and / or dry fibrous structure formed by fibrous elements containing the tinting agents. In one example, the total level of one or more tinting agents present within one or more, for example, a plurality, of fibrous elements of a fibrous structure of the present invention ranges from about 0.0001% to about 0.5% and / or from about 0.0005% to about 0.05% and / or from about 0.001% to about 0.05% and / or from about 0.001% to about 0.005% by weight of the dry fibrous element and / or the dry fibrous structure formed by fibrous elements containing the tinting agents. The tinting agents can be used either alone or in combination. The tinting agents may be selected from any known dyeing chemical class, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including azo, benzodifuran and benzodifuranone premetallized, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof. Non-limiting examples of tinting agents include dyes, dye-clay conjugates and organic and inorganic pigments and mixtures thereof. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling in the Color Index (CI) classifications of Direct, Basic, Reactive or Hydrolyzed Reactive Dyes, Solvent or Dispersion, for example, which are classified as Blue, Purple, Red, Green or Black, and their mixtures. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of color index numbers (Society of Dyers and Colourists, Bradford, UK) of Violet Direct dyes such as 9, 35, 48, 51, 66, and 99, Blue Direct dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Violet Acid dyes such as 15, 17 , 24, 43, 49 and 50, Blue Acid dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Black Acid dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Dispersion or Solvent dyes such as those described in US Patent No. 2008/034511 A1. or US 8,268,016 B2, or the dyes as described in US Pat. No. 7,208,459 B2, and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Acid Violet Acid 17, Blue Dirty 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
[0035] Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently linked chromogens (sometimes referred to as conjugates), (dye-polymer conjugates), for example, polymers with copolymerized chromogens in the polymer backbone and their mixtures. Polymeric dyes include those described in WO2011 / 98355, U.S. Patents 2012/225803 A1, U.S. 2012/090102 A1, U.S. 7,686,892 B2, and WO2010 / 142503. In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of commercially available tinting agents under the trade name Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and their mixtures. In yet another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® Violet CT, carboxymethylcellulose (CMC) covalently bound to a reactive blue dye, reactive violet or reactive red, such as CMC conjugated with Blue Reagent Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-AC ™, alkoxylated triphenyl methane polymer dyes, thiophene alkoxylated polymer dyes, and mixtures thereof.
[0036] In one example, a fibrous structure of the present invention comprising fibrous elements, such as filaments, comprising a tinting agent, has a whiteness index greater than 72 and / or greater than 75 and / or greater than 77 and / or greater at 80 as measured according to the whiteness index test method described herein.
[0037] Solid Additives The fibrous structures and / or sanitary tissue products of the present invention may further comprise one or more solid additives. A "solid additive" as used herein means an additive that is capable of being applied to a surface of a fibrous structure and / or a nonwoven substrate of the fibrous structure in a solid form. In other words, the solid additive of the present invention can be delivered directly to a surface of the fibrous structure and / or the nonwoven substrate of the fibrous structure without any liquid phase present, that is to say without melting the additive solid and without suspending the solid additive in a vehicle or a liquid carrier. As such, the solid additive of the present invention does not require a liquid state or a carrier or a liquid carrier to be delivered to a surface of a nonwoven substrate. The solid additive of the present invention may be delivered via a gas or gas combinations. In one example, in simple terms, a solid additive is an additive that, when placed in a container, does not conform to the shape of the container. In one example, a solid additive comprises naturally occurring fiber such as pulp fiber. Non-limiting examples of suitable solid additives include hydrophilic inorganic particles, hydrophilic organic particles, hydrophobic inorganic particles, hydrophobic organic particles, naturally occurring fibers, naturally occurring particles, and naturally occurring fibers. In one example, naturally occurring fibers may include wood pulp fibers, trichomes, downties, protein fibers, such as silk and / or wool, and / or cotton linters. In one example, the solid additive comprises chemically treated pulp fibers. Non-limiting examples of chemically treated pulp fibers are commercially available from Georgia-Pacific Corporation. In another example, non-naturally occurring fibers may comprise polyolefin fibers, such as polypropylene fibers and / or polyamide fibers.
[0038] In another example, the hydrophilic inorganic particles are selected from the group consisting of: clay, calcium carbonate, titanium dioxide, talc, aluminum silicate, calcium silicate, alumina trihydrate, activated carbon, calcium sulfate, glass microspheres, diatomaceous earth and mixtures thereof. In one example, the hydrophilic organic particles of the present invention may include hydrophobic particles whose surfaces have been treated with a hydrophilic material. Non-limiting examples of such hydrophilic organic particles include polyesters, such as polyethylene terephthalate particles that have been surface-treated with an antifouling polymer and / or a surfactant. Another example is a polyolefin particle which has been surface treated with a surfactant. In another example, the hydrophilic organic particles may comprise superabsorbent particles and / or superabsorbent materials such as hydrogels, hydrocolloidal materials and mixtures thereof. In one example, the hydrophilic organic particle comprises a polyacrylate. Other non-limiting examples of suitable hydrophilic organic particles are known in the art. In another example, the hydrophilic organic particles may comprise high molecular weight starch particles (high amylose starch particles), such as Hylon 7 available from National Starch and Chemical Company. In another example, the hydrophilic organic particles may comprise cellulose particles. In another example, the hydrophilic organic particles may comprise compressed cellulose sponge particles. In an example of a solid additive according to the present invention, the solid additive has a surface tension greater than about 30 and / or greater than about 35 and / or greater than about 40 and / or greater than about 50 and / or greater than about 60 dynes / cm as determined by ASTM D2578. The solid additives of the present invention may have different geometries and / or cross-sections which may be, in particular, round, elliptical, star-shaped, rectangular, trilobal and various other eccentricities. In one example, the solid additive may have a particle size of less than 6 mm and / or less than 5.5 mm and / or less than 5 mm and / or less than 4.5 mm and / or less than 4 mm and / or less than 2 mm in their maximum dimensions. "Particle" as used herein means an object having an aspect ratio of less than about 25/1 and / or less than about 15/1 and / or less than about 10/1 and / or less to 5/1 up to about 1/1. A particle is not a fiber as defined here. The solid additives may be present in the fibrous structures of the present invention at a level greater than about 1 and / or greater than about 2 and / or greater than about 4 and / or up to about 20 and / or up to about about 15 and / or up to about 10 g / m2. In one example, a fibrous structure of the present invention comprises from about 2 to about 10 and / or from about 5 to about 10 g / m 2 of a solid additive.
[0039] In one example, the solid additives are present in the fibrous structures of the present invention at a level greater than 5% and / or greater than 10% and / or greater than 20% up to about 50% and / or up to about 40% and / or up to about 30% by weight of solid additive based on the weight of the fibrous structure.
[0040] Template Material The fibrous structure and / or a sanitary tissue product may further comprise a scrim material. The scrim material may comprise any suitable material capable of bonding to a nonwoven substrate of the fibrous structure of the present invention. In one example, the scrim material comprises a material that can be thermally bonded to the nonwoven substrate of the fibrous structure of the present invention. Non-limiting examples of suitable scrim materials include filaments of the present invention. In one example, the scrim material includes filaments that include hydroxylated polymers. In another example, the scrim material includes starch filaments. In yet another example, the scrim material comprises filaments comprising a thermoplastic polymer. In yet another example, the scrim material comprises a fibrous structure according to the present invention wherein the fibrous structure comprises filaments comprising hydroxylated polymers, such as starch filaments and / or thermoplastic polymers. In another example, the scrim material may comprise a film. In another example, the scrim material may comprise a nonwoven substrate according to the present invention. In yet another example, the scrim material may comprise a latex. In one example, the scrim material may have the same composition as the nonwoven substrate of the fibrous structure. The scrim material may be present in the fibrous structures of the present invention at a basis weight greater than 0.1 and / or greater than 0.3 and / or greater than 0.5 and / or greater than 1 and / or greater at 2 g / m 2 and / or less than 10 and / or less than 7 and / or less than 5 and / or less than 4 g / m 2, as determined by the surface mass test method described herein.
[0041] Methods of the Present Invention The methods of the present invention relate to the production of polymeric structures, for example, fibrous elements, such as filaments, from aqueous molten hydroxyl polymer compositions comprising a fibrous element forming polymer. , such as a hydroxylated polymer, a crosslinking agent, such as dihydroxyethylene-urea (DHEU) and a dual-use material, such as ammonium diester sulfosuccinate salt and / or iminium. Fibrous Structure Manufacturing Processes Figures 1 and 2 illustrate an exemplary method of manufacturing a fibrous structure of the present invention. As shown in Figures 1 and 2, the method 10 comprises the steps of: a. providing first filaments 12 from a first source 14 of filaments, which form a first layer 16 of filaments; b. providing second filaments 18 from a second source 20 of filaments, which form a second layer 22 of filaments; vs. providing third filaments 24 from a third source 26 of filaments, which form a third layer 28 of filaments; d. providing solid additives from a source 32 of solid additives; e. providing fourth filaments 34 from a fourth source 36 of filaments, which form a fourth layer 38 of filaments; and F. collecting the first, second, third and fourth filaments 12, 18, 24, 34 and the solid additives 30 to form a fibrous structure 40, wherein the first source 14 of filaments is oriented at a first angle α with respect to the machine direction of the fibrous structure 40, the second filament source 20 is oriented at a second angle p with respect to the machine direction, different from the first angle α, the third source 26 is oriented at a third angle 8 with respect to the machine direction, different from the first angle a and second angle (3, and wherein the fourth source 36 is oriented at a fourth angle s with respect to the machine direction, different from the second angle f3 and the third angle δ.
[0042] The first, second and third layers 16, 22, 28 of filaments are collected on a collection device 42, which may be a belt or fabric, with or without the aid of a vacuum box 47. The collection device 42 may be a patterned belt that applies a pattern, such as a non-random repeating pattern, to the fibrous structure 40 during the process of manufacturing the fibrous structure. The first, second and third layers 16, 22, 28 of filaments are collected (for example, one on top of the other) on the collection device 42 to form a multilayer nonwoven substrate 44 on which the additives are deposited. The third layer 38 of filaments can then be deposited on the solid additives 30 to form a scrim 46. The first angle α and the fourth angle s can be identical, for example, 90 ° with respect to the machine direction.
[0043] The second angle [3 and the third angle S can be identical, just the positive and the negative of each other. For example, the second angle [3 may be -40 ° with respect to the machine direction and the third angle 5 may be + 40 ° with respect to the machine direction. In one example, at least one of the first, second and third angles a, [3, 6 is less than 90 ° with respect to the machine direction. In another example, the first angle α and / or the fourth angles are about 90 ° to the machine direction. In yet another example, the second angle [3 and / or the third angle S ranges from about ± 10 ° to about ± 80 ° and / or from about ± 30 ° to about ± 60 ° with respect to the machine direction and / or approximately ± 40 ° with respect to the machine direction. In one example, the first, second and third layers 16, 22, 28 of filaments may be formed into a nonwoven substrate 44 before being used in the process of manufacturing a fibrous structure described above. In this case, the nonwoven substrate 44 will likely be located on a mother roll that may be unwound in the fibrous structure manufacturing process and the solid additives may be deposited directly onto a surface of the nonwoven substrate 44.
[0044] In one example, the step of providing a plurality of solid additives 30 on the nonwoven substrate 44 may be to apply the solid additives 30 by a flow of air using a flow forming device. air. A non-limiting example of a suitable airflow forming device is available from Dan-Web of Aarhus, Denmark.
[0045] In one example, the step of providing the fourth filaments 34 such that the filaments are contacted with the solid additives 30 comprises the step of depositing the fourth filaments 34 so that at least a portion (in a all or substantially all) of the solid additives 30 are contacted with the fourth filaments 34, thereby positioning the solid additives 30 between the fourth filament layer 38 and the nonwoven substrate 44. Once the fourth layer 38 of filaments is in place, the fibrous structure 40 may be subjected to a bonding step which links the fourth filament layer 38 (in this case, the scrim 46) to the nonwoven substrate 44. This bonding step may comprise a thermal bonding. The thermal bonding operation may comprise passing the fibrous structure through a nip zone 40 formed by the thermal bonding rollers 48, 50. At least one of the thermal bonding rolls 48, 50 may comprise a pattern which is applied to the binding sites 52 formed in the fibrous structure 40.
[0046] In addition to being bonded, the fibrous structure can also be subjected to other post-processing operations such as embossing, tuft generation, toothed roll processing, which includes the fibrous structure through a nip area formed between two engaged tooth rolls, moisture imparting operations, generation of free fiber ends, and surface treatment to form a finished fiber structure. In one example, the fibrous structure is subjected to toothed roll processing by passing the fibrous structure through a nip formed by at least one pair of toothed rollers. In one example, the fibrous structure is subjected to toothed roll processing so that ends of free fibers are created in the fibrous structure. The toothed roller treatment may take place before or after the combination of two or more fibrous structures to form a multilayer toilet paper product. If this occurs after, then the multilayer toilet paper product is passed through the nip area formed by at least one pair of toothed rolls. The method of manufacturing a fibrous structure of the present invention can be closely coupled (where the fibrous structure is convoltively wound on a roll prior to carrying out a conversion operation) or directly coupled (where the fibrous structure is non-convoltively wound on a roll before carrying out a conversion operation) to a conversion operation for embossing, printing, deforming, surface-treating, or other post-forming operation known to those skilled in the art. For the purpose of the present invention, direct coupling means that the fibrous structure can pass directly to a conversion operation rather than, for example, being convoltively wound on a roll, and then unrolled to carry out a conversion operation.
[0047] In one example, one or more layers of the fibrous structure according to the present invention may be combined, for example, with glue, with another layer of fibrous structure, which may also be a fibrous structure according to the invention, in order to forming a multilayer sanitary tissue product having a tensile strength ratio of 2 or less and / or less than 1.7 and / or less than 1.5 and / or less than 1.3 and / or less than 1 , 1 and / or greater than 0.7 and / or greater than 0.9, as measured by the elongation / tensile strength / total energy absorbed / tangent modulus test method described herein. In one example, the multilayer sanitary tissue product can be formed by combining two or more layers of a fibrous structure according to the present invention. In another example, two or more layers of a fibrous structure according to the present invention may be combined to form a multilayer sanitary tissue product such that the solid additives present in the fibrous structure layers are adjacent to each of the outer surfaces. multilayer sanitary tissue product. The method of the present invention may include the preparation of individual rolls of fibrous structure and / or sanitary tissue product comprising that one or more fibrous structures that are suitable for use by a consumer. In one example, the sources of the filaments include meltblowing dies that produce filaments from an aqueous hydroxyl polymer composition melted according to the present invention. In one example, as shown in Figure 3, the meltblowing die 54 may comprise at least one filament forming hole 56, and / or 2 or more rows, and / or 3 or more rows of forming holes. filaments 56 from which the filaments are spun. At least one row of filament forming holes 56 contains 2 filament forming holes 56 or more and / or 3 or more and / or 10 or more. In addition to the filament forming holes 56, the meltblowing die 54 includes fluid release holes 58, such as gas release holes, in one example of the air release holes, which provide attenuation. to the filaments formed from the filament forming holes 56. One or more fluid release holes 58 may be associated with a filament forming hole 56 such that the fluid exiting the fluid release hole 58 is parallel or substantially parallel (and not slanted as on a knife die) to an outer surface of the filament protruding from the filament forming hole 56. In one example, the fluid exiting the fluid release hole 58 comes into contact with the outer surface of the filament 56. a filament formed from a filament forming hole 56 at an angle of less than 30 ° and / or less than 20 ° and / or less than 10 ° and / or less than 5 ° and / or about 0 °. One or more fluid release holes 58 may be arranged around a filament forming hole 56. In one example, one or more fluid release holes 58 are associated with a single filament forming hole 56 such that the fluid exiting said one or more fluid release holes 58 contacts the outer surface of an individual filament formed from the single filament hole 56. In one example, the fluid release hole 58 allows to a fluid, such as a gas, for example, air, coming into contact with the outer surface of a filament formed from a filament forming hole 56 rather than coming into contact with an inner surface of a filament, as is the case when a hollow filament is formed. ii) Foam Formation The aqueous hydroxyl polymer composition for foaming can be prepared similarly to the formation of fibrous element. The dual-use material solves the same problems as for fiber formation. It may also be advantageous to add a nucleating agent such as microtalc or an alkali metal or an alkaline earth metal salt such as sodium sulfate or sodium chloride in an amount of about 1 to 8% of the weight of the starch. The foam can be shaped into various shapes. iii) Coating Formation The aqueous hydroxyl polymer composition melted for coating formation can be prepared by adding a methylated melamine formaldehyde resin such as Astromel 400 available from Momentive to an aqueous solution of hydroxyl-containing polymer such as a hydroxyethyl acrylate polymer. An aqueous molten hydroxyl polymer composition The aqueous molten hydroxyl polymer composition of the present invention from which the hydroxyl polymer filaments are produced comprises a melt-processed fibrous element forming polymer, such as a hydroxyl-treated polymer. melting, for example, a melt-treated polysaccharide, and a crosslinking system comprising a crosslinking agent and a dual-use material, such as ammonium and / or iminium sulfosuccinate diester salt, according to the present invention. invention. The aqueous molten hydroxyl polymer compositions may already be formed or a melt processing step may be required to convert a fibrous element forming polymer starting material, such as a polysaccharide, into a polymer forming polymer. melt-processed fibrous element, such as a melt-treated polysaccharide, thereby producing the aqueous hydroxyl polymer melt composition. A treatment temperature peak to bring the molten hydroxylated aqueous polymer composition to a temperature between 170 ° C and 175 ° C should be applied to the aqueous molten hydroxyl polymer composition. This can be achieved by heating through the barrel heating of a twin screw extruder or by using a shell in a tube heat exchanger. The aqueous composition of molten hydroxyl polymer should be maintained at 170 to 175 ° C for 1 to 2 minutes. If the molten hydroxylated aqueous polymer composition is at a temperature peak between 170 and 175 ° C for a residence time longer than 2 minutes, undesirable side reactions may occur. Thus, it is important to cool the aqueous hydroxyl polymer composition very rapidly using a rapid quenching process, such as flashing of the aqueous phase. The crosslinking agent is added to the aqueous hydroxyl polymer composition melted after the cooling step. A suitable melt processing step known in the art can be used to convert the fibrous element-forming polymer starting material, for example, the polysaccharide, to the melt-processed fibrous element forming polysaccharide. "Fusion processing" as used herein means any operation and / or any process whereby a polymer is softened to such a degree that it can be brought to a fluid state. The aqueous molten hydroxyl polymer compositions of the present invention may have a shear viscosity, as measured by the shear viscosity measurement method of an aqueous molten hydroxyl polymer composition described herein, of about 0, 5 Pascal seconds to about 25 Pascals seconds and / or about 2 Pascals seconds to about 20 Pascals seconds and / or about 3 Pascals seconds to about 10 Pascals seconds as measured at a rate of shear rate of 3000 s-1 and at the processing temperature of (50 ° C to 100 ° C). The aqueous molten hydroxyl polymer compositions may have a n-value of the thinning index as measured by the shear viscosity measurement method of an aqueous molten hydroxyl polymer composition described herein ranging from about 0.4 to about 1.0 and / or from about 0.5 to about 0.8. The aqueous hydroxyl polymer compositions may have a temperature of about 50 ° C to about 100 ° C and / or about 65 ° C to about 95 ° C and / or about 70 ° C to about 90 ° C when spinning filaments from the aqueous hydroxylated polymer compositions. In one example, the aqueous molten hydroxyl polymer composition of the present invention may comprise about 30% and / or about 40% and / or about 45% and / or about 50% to about 75% and / or about 80% and / or about 85% and / or about 90% and / or about 95% and / or about 99.5% by weight of the aqueous hydroxyl polymer composition melted from a fibrous element forming polymer, such as a polysaccharide. The fibrous element forming polymer, such as a polysaccharide, can have a weight average molecular weight of greater than 100,000 g / mol, as determined by the weight average molecular weight test method described herein, before any crosslinking. A dual-use material may be present in the aqueous molten hydroxyl polymer compositions and / or may be added to the aqueous molten hydroxyl polymer composition prior to the polymeric treatment of the aqueous molten hydroxyl polymer composition.
[0048] A non-hydroxylated polymer, such as a copolymer based on polyacrylamide and / or acrylamide, may be present in the aqueous hydroxyl polymer melt composition and / or may be added to the aqueous hydroxyl polymer composition melt before polymer treatment of the aqueous hydroxyl polymer composition is melted. A tinting agent may be present in the aqueous molten hydroxyl polymer compositions and / or may be added to the aqueous molten hydroxyl polymer composition prior to the polymeric treatment of the molten hydroxylated aqueous polymer composition. Non-limiting Examples The materials used in the examples are as follows: CPI 050820-156 is an acid-diluted tooth corn starch with a weight average molecular weight of 2,000,000 g / mol supplied by Corn Products International, Westchester, IL.
[0049] Hyperfloc NF301, a nonionic polyacrylamide (PAAM) has a weight average molecular weight of between 5,000,000 and 6,000,000 g / mol, and is supplied by Hychem, Inc., Tampa, FL. MA-80-PG Aerosol is an anionic surfactant based on sodium dihexylsulfosuccinate supplied by Cytec Industries, Inc., Woodland Park, NJ. Sulfosuccinic ammonium acid (bis-2-ethylhexyl ester) is prepared via two methods described in Examples 1 and 2, respectively, below. Sulfosuccinic ammonium acid (bis-isobutyl ester) is prepared according to Example 3.
[0050] Example 1 Synthesis of 50% of Sulfosuccinic Ammonium Acid (bis-2-ethylhexyl ester) from Sulfosuccinic Acid (sodium bis-2-ethylhexyl) Sodium 406 g of Dioctyl Sulfosuccinate Diester Sodium Salt are dissolved (98% from Aldrich) in 600 mL of dichloromethane. Ammonium chloride (462 g) is dissolved in 1387 ml of water (25% solution). Both solutions are vigorously stirred in a 4 L beaker and transferred to three 1 L separatory funnels. The emulsion begins to separate within a few minutes. After standing overnight, the organic layer is isolated and evaporated with rotary evaporation (410 mm vacuum, 45 ° C water bath T) until a liquid with a slight dichloromethane odor has developed. to boil. A solution of 132 g of propylene glycol: 168 g of water is added to the solution of sulphosuccinate and evaporated with rotary evaporation (360 mm, water bath at 50 ° C.) to give the ammonium sulphosuccinic acid (bis-sulphate ester). 2-ethylhexyl), 708 g.
[0051] Example 2 Synthesis of 50% of Sulfosuccinic Ammonium Acid (bis-2-ethylhexyl ester) from maleic acid (bis-2-ethylhexyl ester) Di-2-ethylhexyl maleate (90% from Aldrich) ( 300 g, 0.88 mol), ammonium bisulfite (45% from Pfaltz and Bauer) (200.52 g, 0.91 mol) and ammonium sulfosuccinic acid (bis-2-ethylhexyl ester) ( from Example 1) (21 g) are loaded into a 1 L four-necked flask equipped with a mechanical stirrer, a temperature probe attached to a control device for heating the mantle and a condenser with a nitrogen line. The two-phase reaction mixture was stirred with gentle reflux (105 ° C) for 7 hours to give a single phase of sulfosuccinic ammonium acid (bis-2-ethylhexyl ester). Example 3 - synthesis of ammonium sulfosuccinic acid (bis-isobutyl ester) Ammonium chloride was dissolved in 1078 mL of water with heating in a 4L Erlenmeyer flask. Next, 825 g of Aerosol IB ( a sodium diisobutyl sulfosuccinate surfactant (45% from Cytec) to the ammonium chloride solution together with 600 mL of dichloromethane. The suspension is stirred vigorously for 10 minutes to give a white emulsion which is transferred into three 1000 ml separatory funnels. The emulsion begins to separate within a few minutes. After standing overnight, the organic layer is isolated and evaporated with rotary evaporation (410 mm vacuum, 45 ° C water bath T) until a liquid with a slight dichloromethane odor is obtained. Water (300 mL) is added and the solution is rotoevaporated to remove residual dichloromethane (325 mm, 55 ° C water bath) to give 819.27 g of a 44% solution. sulfosuccinic ammonium acid (bis-isobutyl ester). Example 4 - Comparative Example In a 40: 1 APV Baker twin screw extruder ("baking extruder") with eight temperature zones, shown in FIGS. 4A and 4B, starch CPI 050820-156 fibrous element) is mixed with 35% ammonium methanesulphonate (crosslinking agent), 80% Aerosol MA-80-PG surfactant (fast wetting surfactant) and water in zone 1. This mixture is then transported down the barrel through zones 2 to 8 and fired to form a melt-treated hydroxyl polymer composition. The composition in the extruder is 35% water in which the solids composition is 98% CPI 050820-156, 0.8% Aerosol MA-80-PG surfactant and 0.8% methanesulfonate. 'ammonium. The extruder barrel temperature set point values for each zone are shown in Table 1 below: Zone 1 2 3 4 5 6 7 8 Temperature (° C) 15 15 15 50 160 160 185 185 Table 1 The temperature of the extruder barrel the aqueous molten hydroxyl polymer composition leaving the 40: 1 extruder is between 148 and 152 ° C. From the extruder, the aqueous molten hydroxyl polymer composition is fed to a Mahr gear pump and then fed to a second extruder (a "flash extruder"), an example of which is shown in Figures 5A and 5B. The second extruder is a 13:01 APV Baker twin-screw extruder, which serves to cool the melt by venting a stream at atmospheric pressure. The second extruder also serves as a location for the additives to the molten hydroxylated aqueous polymer composition. In particular, a current of 2.2% by weight of hyperfloc polyacrylamide NF301 (non-hydroxylated polymer) is introduced at a rate of 0.3% on a solids basis. Material that is not vented is transported down the extruder to a second Mahr melt pump. From there, the aqueous hydroxyl polymer melt composition is fed to a series of static mixers where 20% DHEU crosslinking agent and water are added. The aqueous hydroxyl polymer composition melted at this point in the process contains 50 to 55% total solids. On a solids basis, the aqueous composition of molten hydroxyl polymer is 93.5% CPI starch 050820-156, 4.2% DHEU crosslinking agent, 0.8% ammonium methanesulfonate, 0.8% Aerosol MA-80-PG surfactant and 0.3% Hyperfloc NF301 PAAM. From the static mixers, the molten hydroxylated aqueous polymer composition is fed to a meltblowing die via a melt pump. Polysaccharide filaments are produced from the aqueous hydroxyl polymer composition melted by the meltblowing die. The filaments are collected on a collection device, such as a belt, for example, a pattern belt, to produce a fibrous structure. Specifically, the following equipment and equipment operating parameters were used to process the aqueous hydroxyl polymer composition melted into a fibrous element. As shown in Figure 6, the aqueous hydroxyl polymer composition present in an extruder 102 is pumped to a die 104 using a pump 103, such as a Zenith®, PEP II type, having a capacity of 10 cubic centimeters. per turn (cc / revolution), manufactured by Parker Hannifin Corporation, Zenith Pumps Division, Sanford, NC, USA. The flow of the aqueous hydroxyl polymer composition melted to the die 104 is controlled by adjusting the number of revolutions per minute (rpm) of the pump 103. Pipes connecting the extruder 102, the pump 103, the die 104, and optionally a mixer 116 are electrically heated and thermostatically controlled at 65 ° C.
[0052] The die 104 has several rows of circular extrusion nozzles 200 spaced from each other at a pitch P (Fig. 7) of about 2,489 millimeters (about 0.098 inches). The nozzles are arranged in a staggered grid with a spacing of 2.489 millimeters (about 0.098 inches) within the rows and a spacing of about 0.085 inches (2.159 millimeters) between the rows. The nozzles 200 have individual internal diameters D2 of about 0.254 millimeters (about 0.010 inches) and individual outside diameters (D1) of about 0.813 millimeters (about 0.032 inches). Each individual nozzle 200 is surrounded by an annular orifice 250 formed in a plate 260 (Figures 7 and 8) having a thickness of about 1.9 mm (about 0.075 inches). A pattern of a plurality of the orifices 250 in the plate 260 corresponds to a pattern of the extrusion nozzles 200. Once the orifice plate is combined with the dies, the resulting surface for the air flow is about 36 percent. The plate 260 is fixed such that the embryonic filaments 110 which are extruded through the nozzles 200 are surrounded and attenuated by generally cylindrical humidified air streams supplied through the orifices 250. The nozzles may extend at a distance of about 250.degree. about 1.5 mm to about 4 mm, and more specifically about 2 mm to about 3 mm, beyond a surface 261 of the plate 260 (Fig. 7). As shown in Fig. 9, a plurality of limiting air ports 300 are formed by connecting the nozzles of two outer rows on each side of the plurality of nozzles, in plan view, so that each boundary layer orifice comprises an annular opening 250 described above. In addition, every other line and column on two of the remaining capillary nozzles are blocked, which increases the spacing between the active capillary nozzles. As shown in Fig. 6, attenuation air may be provided by heating the compressed air from a source 106 by an electrical resistance heater 108, for example, a heater manufactured by Chromalox, Division of Emerson Electric, Pittsburgh, PA, USA. An appropriate amount of water vapor 105 at an absolute pressure of between about 240 and about 420 kilopascals (kPa), controlled by a globe valve (not shown), is added to saturate or substantially saturate the heated air at conditions in the electrically heated feed pipe with thermostatic control 115. The condensate is discharged into an electrically heated separator with thermostatic control 107. The attenuation air has an absolute pressure ranging from about 130 kPa to about 310 kPa, measured in the Hose 115. Extruded filaments 110 have a moisture content of from about 20% and / or from about 25% to about 50% and / or about 55% by weight. The filaments 110 are dried by a drying air stream 109 having a temperature of about 149 ° C (about 300 ° F) to about 315 ° C (about 600 ° F) by an electric resistance heater ( not shown) provided by drying nozzles 112 and discharged at an angle generally perpendicular to the general orientation of the extruded embryonic fibers. The filaments 110 are dried from a moisture content of about 45% to a moisture content of about 15% (i.e., from a consistency of about 55% up to a consistency of about 85%) and are collected on a collection device 111, such as, for example, a porous mobile belt.
[0053] The process parameters are as indicated in Table 2 below. Sample Units Atomizing airflow G / min 9000 Attenuation air temperature ° C 65 Attenuation vapor flow G / min 1,800 Manometric pressure of attenuation vapor kPa 213 Manometric pressure of attenuation in release pipe kPa 14 Attenuation output temperature ° C 65 Solution pump speed RPM 12 Solution flow rate g / min / hole 0.18 Drying airflow g / min 17,000 Driving type Air notches Air pipe dimensions mm 356 x 127 Speed through the pitot-static tube M / s 65 Drying air temperature at heating ° C 260 Position of the drying line from the die mm 80 Angle of the drying line with respect to the fibers degrees 0 Spacing between the drying lines mm 205 Sample Units Distance between the die and the forming box mm 610 Length of the machine direction of the forming box mm 635 Width of the cross direction of the box mm 380 Flow rate of the box g / min forming 41,000 Table 2 Fibrous elements are formed from the molten hydroxylated aqueous polymer composition according to the present invention. The fibrous elements are formed at drying air rates (21,620 g / min) and are collected on a moving porous belt. Vacuum is used to remove the air while letting the fibers form as a fibrous structure on the belt. The belt transports the fibrous structure to the next equipment, all operating at about 0.20 meters / second (40 feet / minute). The fibrous structure feeds through a thermal bonding contact line consisting of two heated metal rollers. The rolls have a diameter of 0.133 meters and are heated to about 199 ° C (390 ° F). One roll is smooth, the other has square protuberances representing 12.8% of the area; the protuberances have a width of 0.508 mm on a grid of 1.499 mm. The rollers are loaded with about 18,900 Newtons per linear meter of roll (about 108 pounds per linear inch). The fibrous structure continues to a heating furnace to harden the fibrous structure. The fibrous structure is supported on an independent porous belt and feeds through a 1,054 meter long furnace operating at 206 ° C (403 ° F) circulating approximately 13,600 grams per minute of heated air. The heat transfer to the polymer structure and thus the temperature of the polymer structure is a function of the air flow rate and the air temperature. The curing temperature can be obtained by adjusting the air flow and the air temperature. The fibrous structure continues to another porous belt where the fibrous structure is moistened to about 7 percent moisture by the addition of steam. The steam is supplied by an Armstrong International 9000 series conditioned steam humidifier. Finally, the fibrous structure is wound on a paper core.
[0054] The cured fibrous structure is characterized by a basis weight, an initial total wet tensile, a maximum total dry absorbed energy and a dry tensile strength and a fiber diameter according to their respective test methods described herein.
[0055] Prior to the test, the samples are conditioned overnight at a relative humidity of 48% to 50% and in a temperature range of 22 ° C to 24 ° C. The resulting fibrous structure has a basis weight of 24 g / m 2, a total energy absorbed at break (TEA) of 12 N / m (31 g / in), a total dry tensile strength of 188 N / m (488 g / m 2). in), an 18% elongation and an initial total wet traction of 17 N / m (45 g / in) and a fiber diameter of 7.19 Ftm. Conductivity of a 1% aqueous suspension = 137.6 microsiemens as measured by their respective test methods described herein.
[0056] EXAMPLE 5 - EXAMPLE OF THE INVENTION An aqueous composition of molten hydroxyl polymer is prepared as described in Example 4 except that the starch OEI 050820-156 (fibrous element forming polymer) is mixed with 50% bis (ethyl 2-ethylhexyl) ammonium sulfosuccinate (dual-purpose material) instead of both ammonium methanesulfonate (crosslinking aids) and Aerosol MA-80- PG (fast wetting surfactant), and water in zone 1. This mixture, on a solids basis, is converted to the aqueous molten hydroxyl polymer composition consisting of 93.5% CPI starch 050820- 156, 4.2% DHEU crosslinking agent, 0.8% ammonium bis (ethyl ester 2-ethylhexyl) sulfosuccinate (dual-use material) and 0.3% Hyperfloc NF301 PAAM (non-hydroxylated polymer) , spun into fibrous elements, and converted to a fibrous structure having a basis weight of 24 g / m 2, a e total absorbed energy (11, A) at break of 18 N / m (47 g / in), a total dry tensile strength of 176 N / m (456 g / in), and an elongation of 27% and an initial total wet tensile of 20 N / m (51 g / po) and a fiber diameter of 6.74 μm Conductivity of a 1% aqueous suspension = 58.9 microsiemens as measured by their respective test methods described here. Example 6 - Example of the Invention An aqueous hydroxyl polymer polymer composition is prepared as described in Example 4, except that the starch OEI 050820-156 (fibrous element forming polymer) is mixed with 50% ammonium bis (isobutyl ester) sulfosuccinate (dual-use material) instead of both ammonium methanesulfonate (crosslinking aids) and Aerosol MA-80-PG surfactant ( fast wetting surfactant), and water in zone 1. This mixture, on a solids basis, is converted into the aqueous composition of molten hydroxylated polymer consisting of 93.5% CPI starch 050820-156, 4.2% DHEU crosslinking agent, 0.8% ammonium bis (isobutyl ester) sulfosuccinate, and 0.3% Hyperfloc NF301 PAAM (non-hydroxylated polymer), spun into fibrous elements, and converted into a fibrous structure having a basis weight of 24 g / m 2, a total absorbed energy (TEA) at 1 has a 19 N / m (49 g / in) rupture, a total dry traction of 234 N / m (606 g / in), and an elongation of 23% and an initial total wet traction of 21 N / m m (54 g / in) and a fiber diameter of 6.96 μm. Conductivity of a 1% aqueous suspension = 77.0 microsiemens as measured by their respective test methods described herein. Test Procedures Unless otherwise specified, all tests described herein, including those described under the Definitions section and the following test procedures, are performed on samples that have been conditioned in a conditioned room at a temperature of 23 ° C ± 1.0. a relative humidity of 50% ± 2% for a minimum of 24 hours before the test. All plastic and cardboard packaging materials, if any, must be carefully removed from the samples prior to testing. The tested samples are "usable units". "Usable units" as used herein refers to sheets, flat portions from a roll stock, pre-processed flat portions, a fibrous structure, and / or monolayer or multilayer products. Unless otherwise indicated, all tests are carried out in such an air-conditioned room, all tests are carried out under the same environmental conditions and in such an air-conditioned room. Eliminate any damaged product. Do not test samples that have defects such as creases, tears, holes, and the like. All instruments are calibrated according to the manufacturer's specifications. Conductivity test method A sample of 3 g of filaments and / or fibrous structure and / or hygienic paper product is milled in an IKA mill for 1 minute. A 1% suspension was prepared with 1.00 g of the crushed filaments and / or fibrous structure in deionized water. The sample was magnetically stirred for 5 minutes and the conductivity was determined with a VWR - Control Company conductivity meter or equivalent conductivity meter with an accuracy of ± 2% in microsiemens. Surface mass test method The basis weight of a fibrous structure and / or a sanitary tissue product is measured on stacks of twelve usable units using a top loading analytical balance with a resolution of ± 0.001 g . The scale is protected from drafts and other disturbances by using a draft protection screen. A precision die is used, measuring 8.890 cm ± 0.00889 cm on 8.890 cm ± 0.00889 cm to prepare all samples. With a precision die cut, cut the samples into squares. Combine the cut squares to form a stack with a thickness of twelve samples. Measure the mass of the sample stack and record the result at plus or minus 0.001 g. The basis weight is calculated in g / m2, as follows: Area weight = (Mass of the pile) / [(Area of 1 square in the pile) x (Number of squares in the stack)] Weight per area (g / m2) = Mass of the stack (g) / [79.032 (cm2) / 10,000 (cm2 / m2) x 12] Indicate the result at plus or minus 0.1 g / m2. The dimensions of the sample may be varied or varied using a similar precision cutting member as mentioned above, so as to have at least 645 square centimeters of sample area in the stack.
[0057] Calibration method The caliper of a fibrous structure and / or a sanitary tissue product is measured using a ProGage micrometer (Thwing-Albert Instrument Company, West Berlin, NJ) with a pressure foot diameter of 5. 8.0 cm (2.20 inches (3.14 in.) Area) at a pressure of 14.725 g / cm2 (95 g / in2) Four (4) samples are prepared by cutting one unit Usable so that each cut sample is at least 6.35 centimeters (2.5 inches) per side, avoiding obvious creases, folds and defects An individual test piece is placed on the anvil by centering it under the foot of The foot is lowered to 0.0762 cm / s (0.03 in / s) at an applied pressure of 14.725 g / cm2 (95 g / in2) Measurement is taken after a hold time of 3 s, The measurement is repeated in the same way for the remaining 3 samples, and the thickness is calculated as the thickness. the average of the four specimens and is expressed in mils (0.00254 cm (0.001 inch)) to 0.0003 mm (0.1 mil). Density test method The density of a fibrous structure and / or a sanitary tissue product is calculated as the quotient of the basis weight of a fibrous structure or a toilet tissue product expressed in pounds / 3,000 square feet divided by the size (14.725 g / cm2 (95 g / in2)) of the fibrous structure or toilet paper product expressed in mils. The final density value is calculated in pounds / feet3 and / or g / cm3, using the appropriate conversion factors.
[0058] Medium Density Test Method A fibrous structure comprising filaments of appropriate mass per unit area (approximately 5 to 20 grams / square meter) is cut into a rectangular shaped sample of approximately 20 mm by 35 mm. The sample is then coated using a SEM sputter coating device (EMS Inc, PA, USA) with gold to make the filaments relatively opaque. The typical thickness of the coating is between 50 and 250 nm. The sample is then mounted between two standard microscope slides and compressed using small leaf tweezers. The sample is observed using a 10x lens on an Olympus BHS microscope with the microscope's light collimation lens shifted as far as possible from the lens. Images are captured using a Nikon Dl digital camera. A glass microscope micrometer is used to calibrate the spatial distances of the images. The approximate resolution of the images is 1! Mi / pixel. The images generally show a distinct bimodal distribution in the intensity histogram corresponding to the filaments and the background. Camera settings or different surface weights are used to obtain an acceptable bimodal distribution. Typically, we take 10 images per sample and average the results of image analysis.
[0059] The images are analyzed in a manner similar to that described by B. Pourdeyhimi, R. and R. Dent in "Measuring fiber diameter distribution in nonwovens" (Textile Res., J. 69 (4) 233-236, 1999). Digital images are analyzed by computer using MATLAB (Version 6.1) and the MATLAB Image Processing Tool Box (Version 3). The image is first converted to a gray scale. The image is then binarized into black and white pixels using a threshold value that minimizes the intraclass variance of black and white thresholded pixels. Once the image has been binarized, the image is skeletonized to locate the center of each fiber in the image. The distance transform of the binarized image is also calculated. The scalar product of the skeletonized image and the distance map provides an image whose pixel intensity is either zero or the radius of the fiber at that location. Pixels within a radius of the junction between two overlapping fibers are not counted if the distance they represent is less than the radius of the junction. The remaining pixels are then used to calculate a histogram weighted by the length of the filament diameters contained in the image.
[0060] Elongation Test Method / Tensile Strength / Total Absorbed Energy / Tangent Modulus Elongation (stretching), tensile strength, total energy absorbed, and tangent modulus are measured on a tensile modulus the constant extension tensile strength with computer interface (a suitable instrument is the Thwing-Albert Instrument Co. Wet Berlin, NJ EJA Vantage) using a load cell for which the measured forces are included between 10% and 90% of the load cell limit. The movable (upper) and fixed (lower) pneumatic jaws are both equipped with smooth stainless steel claws, with a design suitable for testing a 2.54 cm (1 ") wide sheet material (Thwing-Albert item # 733GC). Air pressure of about 413.68 kPa (60 psi) is supplied to the jaws. Eight usable units of fibrous structures are divided into two stacks of four usable units each. The units that can be used in each stack are always oriented with respect to the machine direction (SM) and the cross direction (ST). One of the batteries is designated for the machine direction test and the other for the cross direction. Using a 2.54 cm (one inch) precision cutting tool (Thwing-Albert JDC-1-10, or similar) take a ST stack and cut a stack of 2.54 cm ± 0.0254 cm strips wide 7.62 to 10.16 cm long (1.00 "± 0.01" wide by 3 "to 4" long) (longitudinal dimension in ST). In the same way, cut the remaining stack in the SM (longitudinal dimension of the strip in the SM), to obtain a total of 8 samples, four bands in the ST and four bands in the SM. Each strip to be tested has a thickness of one usable unit, and will be treated as a unit sample to be tested.
[0061] Program the tensile strength tester to perform an extension test, collecting force and extension data at an acquisition rate of 20 Hz as the crosshead increases at a speed of 5 mph. , 08 cm / min (2.00 po / min) until the sample breaks. The breaking sensitivity is set to 80%, i.e., the test is terminated when the measured force drops to 20% of the maximum peak force, after which the beam is returned to its original position. Set the reference length to 2.54 centimeters (1.00 inches). Zero the crosshead and the load cell. Insert the sample into the open top and bottom claws so that at least 1.28 centimeters (0.5 inches) of the sample is contained in each claw. Align the sample vertically in the upper and lower jaws, then close the top claw. Check that the sample is aligned, then close the bottom claw. The sample should be relatively straight between the claws, with no more than 0.05 N (5.0 g force) on the load cell. Add a pre-tension force of 0.03 N (3 g). This voltage is applied to the sample to define the adjusted reference length, and by definition is the point of zero stress. Start the traction tester and collect the data. Repeat the test in the same way for all four ST and four SM samples. Program the software to calculate the following elements from the force-built curve (g) according to the extension (po). Eight samples were analyzed on the tensile strength tester (four in the MS and four in the ST) and the average of the tensile strength in the total dry state, the total energy absorbed Dry breaking and dry breaking stretch respectively is indicated by the tensile strength in the total dry state, the total energy absorbed at break to dryness and the dry breaking stretch. The total energy absorbed at break is defined as the tensile energy absorbed (curve of the area under load as a function of the tensile stress) from a zero stress up to the point of breaking force, with units in g / po. Dry breaking stretch is defined as the percentage of stress measured after the web has been stretched beyond its point of peak loading, where the force drops to exactly 50% of its peak load force.
[0062] The total energy absorbed at dry fracture is then divided by the basis weight of the web from which it was tested to arrive at the total absorbed energy of the present invention, and is calculated as follows: Total energy absorbed = Total energy absorbed at break / Belt mass density (g / m 2) The tensile strengths in the dry state SM and ST are determined using the above-mentioned hardware and calculations as follows.
[0063] The tensile strength is generally the maximum peak force (g) divided by the width of the sample (2.5 cm (1 in)), and indicated in g / inch at plus or minus 0.4 N / m (1 g / in). Mean tensile strength = sum of tensile load (SM) measurements / (Number of tensile belts tested (SM) * Number of usable units or layers per tensile strip) This calculation is repeated for the tests in direction through.
[0064] Tensile strength in the total dry state = average tensile strength SM + average tensile strength ST The tensile strength value in the dry state (DTT) is then normalized for the basis weight of the web from which it has been tested. The standard basis weight used is 24 g / m2, and is calculated as follows: (Standard Dry Traction) = {Dry Traction} * 24 (g / m2) / Belt Weight ( g / m2) The different values are calculated for the four ST samples and the four SM samples. Separately calculate an average for each parameter for the cross-machine and machine direction samples. Total Initial Wet Traction Test Method Cut out tension strips precisely in the direction indicated; four in the machine direction (SM) and four in the transverse direction (ST). Cut the sample strips 4 "(101.6 mm) long and exactly 25.4 mm (1") wide using a Model 240-7A Alpha Precision Sample Cutting Tool ( pneumatic): Thwing-Albert Instrument Co and a suitable matrix. An apparatus for determining the electronic tensile strength (Thwing-Albert EJA Vantage Tester, Thwing Albert Instrument Co., 10960 Dutton Rd., Philadelphia, Pa., 19154) is employed and used at a traverse speed of about 10.16 cm (4.0 inches) per minute, using a strip of fibrous structure 2.54 centimeters (1 inch) wide and about 10.16 centimeters (4 inches) long. The reference length is 2.54 centimeters (1 inch). The band is inserted into the jaws with the section 2.54 centimeters (1 inch) wide in the clamps, ensuring that the sample is hanging well straight into the lower jaw. The sample is then pre-loaded with 7,87 to 19,68 g / cm (20 to 50 g / in) of pre-charge force. This voltage is applied to the band to define the adjusted reference length, and by definition is the point of zero stress. The sample is then wetted thoroughly with water using a syringe to gently apply water to the top of the band sample within the jaws. The movement of the crossbar is then triggered after 3 to 8 seconds after the initial contact with the water. The first result of the test is a data table in the form of the load (grams-force) as a function of the displacement of the crossbar (centimeters from the starting point). The sample is tested in two orientations, referred to herein as SM (machine direction, that is, in the same direction as the continuous take-up reel and the training web), and ST (cross-machine direction). that is, at 90 ° to the SM). The wet tensile strengths in the MS and the ST are determined using the above-mentioned hardware and calculations as follows: Total Initial Wet Traction = I (TpoWuTeelar (ggf / epurr + ce) = Maximum load sm (gf) / 2 Maximum load sT (gf) / 2 (inch) The initial total wet traction value is then normalized for the mass per unit area of the web from which it was tested. g / m 2, and is calculated as: {initial total wet weight} normalized = {initial total wet tensile} * 24 (g / m 2) / web mass per unit (g / m 2) In one example, total initial wet traction of a polymeric structure, such as a fibrous structure, of the present invention is at least 1.18 g / cm (3 g / in) and / or at least 1.57 g / cm (4 g / in) and / or at least 1.97 g / cm (5 g / in) in which case the crosslinking system is accepted. corn. Initial total wet traction may be less than or equal to approximately 23.62 g / cm (60 g / in) and / or less than or equal to approximately 21.65 g / cm (55 g / in) and / or less than or equal to at about 19.69 g / cm (50 g / in)).
[0065] Weight average molecular weight test method The weight average molecular weight (Mw) of a material, such as a hydroxylated polymer, is determined by gel filtration chromatography (GPC) using a mixed bed column. A High Performance Liquid Chromatograph (HPLC) is used with the following components: Millenium® Pump, Model 600E, System Control and Version 3.2 Control Software, Model 717 Plus Autosampler, and CHM- column heater. 009246, all manufactured by Waters Corporation of Milford, MA, USA. The column is a mixed LA lain gel column (the molecular weight of the gel is 1000 g / mol to 40,000,000 g / mol) having a length of 600 mm and an internal diameter of 7.5 mm and the precolumn is a PL 20 μm gel column, length 50 mm, internal diameter 7.5 mm. The column temperature is 55 ° C and the injection volume is 200 μL. The detector is an enhanced optical system (EOS) DAWN® including Astra® software detector software, Version 4,73.04, manufactured by Wyatt Technology of Santa Barbara, CA, USA, a laser light diffraction detector with a K5 cell and a 690 nm laser. Gain on odd-numbered detectors set to 101. Gain on even-numbered detectors set to 20.9. Optilab® Differential Refractometer from Wyatt Technology set at 50 ° C. Gain set to 10. The mobile phase is HPLC grade dimethylsulfoxide with 0.1% w / v LiBr and the mobile phase flow rate is 1 mL / min, isocratic. The execution time is 30 minutes. A sample is prepared by dissolving the material in the mobile phase nominally at 3 mg of material / 1 mL of mobile phase. The sample is capped and then stirred for about 5 minutes using a magnetic stirrer. The sample is then placed in a convection oven at 85 ° C for 60 minutes. The sample is allowed to cool to room temperature without disturbing it. The sample is then filtered through a Spartan-25 type 5 Jim nylon membrane, manufactured by Schleicher & Schuell, of Keene, NH, USA, in a 5 mL autosample vial (mL) using a 5 mL syringe.
[0066] For each measured sample series (3 or more samples of a material), a solvent blank is injected onto the column. Then, a control sample is prepared in a manner similar to that for the samples, described above. The control sample comprises 2 mg / mL pullulan (Polymer Laboratories) having a weight average molecular weight of 47,300 g / mol. The control sample is analyzed before analyzing each set of samples. The tests on the blank, the control sample, and the material test samples are done in duplicate. The final test is a white test. The light diffraction detector and the differential refractometer are used in accordance with the "Dawn EOS Light Scattering Instrument Hardware Manual" and the "Optilab® DSP Interferometric Refractometer Hardware Manual," both manufactured by Wyatt Technology. Corp., of Santa Barbara, CA, USA. The weight average molecular weight of the sample is calculated using the detector software. A dn / dc (differential refractive index difference with concentration) value of 0.066 is used. The baselines for the laser light detectors and the refractive index detector are corrected to eliminate contributions of detector dark current and solvent diffusion. If a laser light detector signal is saturated or has excessive background noise, it is not used in the calculation of the molecular weight. The regions for the characterization of the molecular weight are chosen so that the signals for the 90 ° detector for both the diffraction of the laser light and the refractive index are greater than 3 times their line noise levels. respective basis. Typically, the high molecular weight side of the chromatogram is limited by the refractive index signal and the low molecular weight side is limited by the laser light signal. The weight average molecular weight can be calculated using a "first order Zimm plot" as defined in the detector software. If the weight average molecular weight of the sample is greater than 1,000,000 g / mol, then both first and second order Zimm plots are calculated, and the result with the smallest error of a regression curve is used to calculate the molecular weight.
[0067] The reported weight average molecular weight is the average of the two analyzes of the material test sample. Whiteness Index Test Method The color (in this case whiteness) is measured using a diffuse sphere spectrophotometer / 8 ° (X-Rite SP62). The spectrophotometer is calibrated against white ceramic tile and black ceramic tile according to the manufacturer's instructions and set to calculate Hunter values (L, a, b) with C2 illumination. The color measurement of a fibrous structure is carried out by stacking two or more usable units of the fibrous structure one above the other such that a usable mass of stackable units of at least 100 g / m2 is obtained for the area of the stack of usable units to be measured within the measurement area of the spectrophotometer. The stack of usable units is then placed flat against a white ceramic tile background.
[0068] The absolute color values of the fibrous structure are determined by averaging nine measurements of absolute color value from both the top and bottom surfaces on the stack of usable units. The whiteness index (WI) of the fibrous structure is calculated using the Stensby equation: WI = L - 3b + 3a Measuring method for measuring shear viscosity of an aqueous hydroxyl polymer melt composition Shear viscosity An aqueous molten hydroxyl polymer composition comprising a crosslinking system is measured using a capillary rheometer, Goettfert Rheograph 6000, manufactured by Goettfert USA of Rock Hill SC, USA. The measurements are made using a capillary die having a diameter D of 1.0 mm and a length L of 30 mm (i.e., L / D = 30). The die is attached to the bottom end of the 20 mm rheometer cylinder, which is maintained at a test temperature of 75 ° C. A 60 g sample preheated to the test temperature of the molten hydroxylated aqueous polymer composition is loaded into the cylinder section of the rheometer. Eliminate any trapped air from the sample. Push the sample from the cylinder through the capillary die to a set of speeds selected from 1000 to 10,000 seconds-1. Apparent shear viscosity can be calculated with the rheometer software from the pressure drop experienced by the sample as it passes from the cylinder through the capillary die and sample flow through the capillary die. The log (apparent shear viscosity) can be plotted against the log (shear rate) and the plot can be adjusted by the power law, according to the formula = Kyn-1, where K is the viscosity constant of the material, n is the dilution index of the material, and y is the shear rate. The apparent apparent shear viscosity of the composition is here calculated from interpolation at a shear rate of 3000 s-1 using the power law relationship. Method of pH testing aqueous composition of molten hydroxyl polymer The pH of an aqueous composition of molten hydroxyl polymer is determined by adding 25 ml of the aqueous hydroxyl polymer composition melt to 100 ml of deionized water, stirring with spatula for 1 min and measuring the pH. The dimensions and values described here should not be understood as strictly limited to the exact numerical values quoted. Instead, unless otherwise indicated, each such dimension means both the quoted value and the functionally equivalent range surrounding that value. For example, a dimension described as "40 mm" means "about 40 mm". The quotation from any document is not an admission that it is a prior art in relation to any invention described here or that alone, or in any combination with any which other reference (s) or references, teaches, proposes or describes any such invention. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in any other document, the meaning or definition attributed to that term in this document document will have to prevail.
[0069] While particular embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various other variations and modifications can be made without departing from the spirit and scope of the invention. .

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. A fibrous element comprising a fibrous element forming polymer and a dual-use material, characterized in that the dual-use material has both a crosslinking agent function and a fast wetting surfactant function.
[0002]
A fibrous element according to claim 1, characterized in that the fibrous element forming polymer comprises a hydroxylated polymer; preferably characterized in that the hydroxylated polymer comprises a polysaccharide; more preferably characterized in that the polysaccharide is selected from the group consisting of: starch, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives, cellulose copolymers, hemicellulose, hemicellulose derivatives, hemicellulose copolymers, and mixtures thereof.
[0003]
A fibrous element according to claim 1 or 2, characterized in that the crosslinking agent is selected from the group consisting of: imidazolidinones, polycarboxylic acids and mixtures thereof; preferably characterized in that the crosslinking agent comprises an imidazolidinone; more preferably characterized in that the imidazolidinone is dihydroxy-ethylene-urea.
[0004]
A fibrous element according to any one of the preceding claims, characterized in that the dual-use material comprises one or more of the following compounds: a. an ammonium sulfosuccinate diester salt; b. an iminium sulfosuccinate diester salt; and c. their combinations.
[0005]
5. A fibrous element according to any one of claims 1 to 3, characterized in that the dual-use material is of the following formula I: MO3S OR ROinwhere MO3S consists of 1 4+ and -03S, where M ± is a ammonium or iminium cation, for example, + NHnR24, where n is from 0 to 4 and / or from 0 to 3 and / or from 0 to 2 and / or from 0 to 1 and / or is equal to 0; and R2 is independently selected from the group consisting of: alkyl, hydroxyalkyl, alkanolamine, aryl, hydroxylaryl, or part of a heterocyclic ring, and wherein R is linear or branched C1-C18 alkyl and / or linear alkyl or branched C1 to Cu and / or linear or branched C1 to C8 alkyl; preferably characterized in that R2 is an aliphatic or aromatic N-heterocycle.
[0006]
A fibrous element according to any one of the preceding claims, characterized in that the dual-use material is produced from an amine and a sulfosuccinic acid diester; preferably characterized in that the amine has a boiling point of less than 270 ° C.
[0007]
A fibrous element according to any of claims 1 to 3, characterized in that the dual-use material is selected from the group consisting of: bis (bis-isobutyl ester) ammonium sulfosuccinic acid salt; ammonium salt of sulfosuccinic acid bis (pentyl ester); sulphosuccinic acid bis (2-ethylhexyl ester) ammonium salt wherein the ammonium cation is derived from ammonia, dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, 2-amino-2-methyl-1-propanol, methyldiethanolamine, 4-ethylmorpholine, 4-methylmorpholine, 4,4-dimethyloxazolidine.
[0008]
A fibrous element according to any one of the preceding claims characterized in that the fibrous element further comprises a non-hydroxyl polymer selected from the group consisting of: polyacrylamide and its derivatives; polyacrylic acid, polymethacrylic acid and their esters; polyethylene imine; copolymers made from monomer mixtures of the aforementioned polymers; and their mixtures; preferably, wherein the non-hydroxylated polymer comprises a polyacrylamide.
[0009]
9. fibrous element according to any one of the preceding claims, characterized in that the fibrous element comprises a filament.
[0010]
A fibrous element according to any one of the preceding claims, characterized in that the fibrous element has a mean diameter of less than 50 μm as measured by the average diameter test method.
[0011]
A fibrous element according to any one of the preceding claims, characterized in that the fibrous element is made from an aqueous molten hydroxyl polymer composition comprising the fibrous element forming polymer, the crosslinking agent, and the dual-use material.
[0012]
12. A fibrous structure characterized in that it comprises a plurality of fibrous elements according to any one of the preceding claims.
[0013]
13. A fibrous structure according to claim 12, characterized in that the fibrous structure further comprises one or more solid additives; preferably wherein at least one of the solid additives comprises naturally occurring fiber.
[0014]
A fibrous structure according to claim 13, characterized in that the fibrous structure further comprises a scrim attached to the surface of the fibrous structure such that the solid additives are positioned between the scrim and a surface of a nonwoven substrate fibrous structure.
[0015]
15. A method of manufacturing a fibrous structure characterized in that it comprises the steps of: a. providing an aqueous molten hydroxyl polymer composition comprising a fibrous element forming polymer and a crosslinking system comprising a crosslinking agent and a dual-use material which has both a crosslinking agent function and a crosslinking function. fast wetting surfactant; and B. performing a polymer treatment of the molten hydroxylated aqueous polymer composition such that a plurality of fibrous elements according to any one of claims 1 to 11 is formed; vs. collecting the fibrous elements on a collection device such that a fibrous structure is formed.

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2016-01-25| PLFP| Fee payment|Year of fee payment: 2 |

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2018-07-20| PLSC| Search report ready|Effective date: 20180720 |

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2018-11-30| ST| Notification of lapse|Effective date: 20181031 |

优先权:

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申请号 | 申请日 | 专利标题

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US201461938327P| true| 2014-02-11|2014-02-11|

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