MXPA01003751A - Process for making soft tissue paper - Google Patents

Abstract

A composition is exposed to soften a cellulose structure of wet laying. A particularly preferred structure is a tisuabsorbent. In addition, tissue structures are exposed using the composition. The composition includes an effective amount of a softening active ingredient, a vehicle in which the softening active ingredient is dispersed, an electrolyte dissolved in the carrier, and a bilayer breaking agent. The electrolyte and the bi-layer breaking agent cooperate to cause the viscosity of the composition to be less than the viscosity of a dispersion of the softening active ingredient in the vehicle alone. Preferably, the softening active ingredient is a quaternary ammonium compound with the formula: (R1) 4-m-N + - [(CH2) nY-R3) mX-, the carrier is water, the electrolyte is calcium chloride and the Bilayer breaking agent is a non-ionic surfactant. A method to use the compound when adding it in a concentration of use to the final process of wetting a paper process is also exposed.

Description

i PROCESS TO MANUFACTURE SOFT TISSUE PAPER This is a continuation in part of U.S. Patent Application Series No. 5 60 / 104,371, filed in the name of Vinson, et al., On October 15, 1998, pending.

TECHNICAL FIELD This invention relates, in general, to 10 softening cellulose structures with compounds to inhibit cationic binding; and more specifically, with a composition that has rheological properties that facilitate its use to improve the smoothness thereof. More particularly, the invention relates to smoothing tissue paper webs and methods for producing these smoothed webs.

BACKGROUND OF THE INVENTION 20 Tissue products for toilet paper are widely used. These items are offered commercially in ready-made formats for a variety of uses such as facial tissues, toilet paper and absorbent towels.

All these sanitary products share a common need, specifically to be soft to the touch. Softness is a complex tactile impression evoked by a product when rubbed against the skin. The purpose of being soft is so that these products can be used to clean the skin without being irritating. Effectively cleaning the skin is a persistent personal hygiene problem for many people. Unpleasant discharge of urine, menstruation and fecal matter from the perineal area or discharge of mucus or ordolaryngological do not always occur at a convenient time for someone to perform a total cleaning, as could be with soap and large amounts of water for example. As a substitute for total cleaning, a wide variety of tissue and towel products are offered to assist in the task of removing skin and retaining these discharges in a hygienic manner. Not surprisingly, the use of these products does not approximate the level of cleanliness that can be achieved by most methods for total cleaning and manufacturers of tissue and towel products constantly strive to make their products compete more favorably with the methods for total cleaning. The deficiencies of the tissue products, for example, cause most of the cleaning to stop before the skin is completely cleaned. This behavior is caused by the hardness of the tissue, as it is continued rubbing with a rough implement can abrade or scorch the sensitive skin and cause severe pain. The alternative of allowing the skin to be partially cleaned is chosen, although this often causes bad odors to emanate and can cause the underwear to stain and over time can also cause skin irritations. Anus disorders, for example hemorrhoids, make the perianal area extremely sensitive and cause those suffering from these disorders to be frustrated particularly by the need to clean the anus without causing irritation. Another notable case that causes frustration is to repeatedly blow the nose that is necessary when one has a cold. The repeated cycles of blowing and rubbing can culminate in an inflamed nose even when the softest tissues available today are used. Therefore, providing soft tissue and towel products that promote comfortable cleaning without making harmful sacrifices has been the goal of engineers and scientists who have dedicated themselves to the search for tissue improvement. There have been many attempts to reduce the abrasive effect, that is, to improve the quality of the tissue products. One area that has been exploited with respect to this has been to select and modify the morphologies of the cellulose fiber and the paper structures subjected to engineering to obtain optimum advantages of the available morphologies. The technique applicable in this area includes: Vinson et al. in the United States Patent 5, 228,954, issued July 20, 1993, Vinson in U.S. Patent 5,405,499, issued April 11, 1995, Cochrane et al. in U.S. Patent 4,874,465 issued October 17, 1989 and Hermans et al. in the United States Statutory Invention Record H1672, published on August 5, 1997, all state methods to select or improve fiber sources for tissue and towels of superior properties. The applicable technique is further illustrated by Carstens in U.S. Patent 4,300,981, issued November 17, 1981, which discusses the manner in which fibers can be incorporated to conform to paper structures so that they have a maximum softness potential. While these techniques as illustrated by these prior art examples are widely recognized, they can only offer some limited potential to manufacture tissue implements for truly effective and comfortable cleaning. Another area that has received considerable attention is the addition of chemical softening agents (also referred to herein as "chemical softeners") for "tissue and towel products." In the sense in which it is used herein, the The term "chemical softening agent" refers to any chemical ingredient that enhances the feel sensation perceived by the consumer holding a particular paper product and rubs it through the skin.Although somewhat desirable for towel products, the Softness is a particularly important property for facial tissue and toilet paper.This softness that can be perceived by touch can be characterized in an enunciative way by: friction, flexibility and smoothness, as well as subjective descriptors such as a slippery feeling, velvet, silk or flannel Suitable materials include those that have a slippery feel to the tissue. or includes, for purposes only exemplary, basic waxes such as paraffin and beeswax and oils such as mineral oil and silicone oil as well as petrolatum and more complex emollients and lubricants such as quaternary ammonium compounds with long alkyl chains , functional silicones, fatty acids, fatty alcohols and fatty esters. The field of action in the prior art pertaining to chemical softeners has taken two trajectories. The first trajectory is characterized by the addition of softeners to the tissue paper web during its formation either by adding a binder ingredient to the pulp tubs that will ultimately shape a tissue paper web, to the custom pulp suspension. that approaches a paper machine, or the humid weft according to reside W%? on a Fourdrinier canvas or a drying cloth on a paper machine. The second path is categorized by the addition of chemical softeners to the tissue web after the web dries. Applicable processes can be incorporated into the papermaking operation, such as, for example, by spraying on the dry weft before it is wound onto a roll of paper. The prior art technique related to the above trajectory is categorized by the addition of chemical softeners to the tissue paper prior to assembly into a weft (addition in "the final moistening step"), includes US Pat. No. 5,264,082, issued to Phan and Trokhan on November 23, 1993 and in U.S. Patent 5,543067, issued to Phan on August 6, 1996, the disclosure of each is incorporated herein by reference. These methods have found wide use in the industry. However, these prior art compositions are either solid or viscous liquids at room temperature. As a result, the chemical softening composition of the prior art must be heated before dilution to use the concentration by addition to the pulp. This heating adds complexity to the papermaking process and has an additional capillary requirement for the equipment, necessary. The additional exemplary technique related to the addition of chemical softeners to the tissue paper web during its formation includes U.S. Patent 5,059,282, issued to Ampuiski, et al. on October 22, 1991, incorporated herein by reference. The Ampulski patent discloses a process for adding a polysiloxane compound to a wet tissue web (preferably at a fiber consistency of between about 20% and 35%). This method represents an advance in some aspects with respect to the addition of chemicals in the papermaking pulp. For example, this means is directed to the application of one of the surfaces of the weft as it is opposed to distribute the additive over all the fibers of the pulp. However, when these softening compositions are used, there may be a loss of control of the sheet as it is creped from the Yankee dryer. A widely considered theory is one in which the additives interfere with the coating on the Yankee dryer so that the bond between the wet web and the dryer weakens. Considerable technique has also been directed towards the application of chemical softeners for already dry paper webs, either in the so-called final drying process of the paper machine or in a separate transformation operation subsequent to the step of papermaking. The exemplary technique of this field includes U.S. Patent 5,215,626, issued to Ampulski, et al. on June 1, 1993; U.S. Patent 5,246,545, issued to Ampulski, et al. on September 21, 1993; U.S. Patent 5,525,345, issued to Warner, et al. on June 11, 1996 and U.S. Patent Application Serial No. 09 / 053,319 filed in the name of Vinson, et al. on April 1, 1998, all incorporated herein by reference. Patent? 62ß discloses a method for preparing soft tissue paper by applying a polysiloxane to a dry weft. The '545 patent discloses a similar method using a heated transfer surface. The patent? 345 discloses the methods for the application that include roller coating and extrusion to apply the compositions j & gÉ & safa & amp; amp; a .. particular to the surface of a dry tissue web. Finally, the request of Vinson, et al. exposes the compositions that are particularly suitable for surface application on a tissue web. While each of the references represents advances' with respect to the prior art, there is a continuing need for soft tissue paper products that have good strength properties. There is also a need to improve the softening compositions that can be applied to these tissue products to provide the softness requirement without adding additional complexity and capital expense to the manufacture of these products. These improved products, compositions and methods are provided by the present invention and are shown in the following discussion.

BRIEF DESCRIPTION OF THE INVENTION The present invention describes softening compositions which, when added to the final wetting step of a wet laying process to produce cellulosic structures, reduce fiber-to-fiber bonding thereof, providing a structure that improves the softness while providing acceptable strength and absorbency. The softening composition comprises: an effective amount of a softening active ingredient; a vehicle in which the softening active ingredient is dispersed; an electrolyte dissolved in the vehicle, the electrolyte causes the viscosity of the composition to be less than the viscosity of a dispersion of the softening composition in the vehicle alone; and a bi-layer breaking agent to further reduce the viscosity of the softening composition. The term "cellulosic structure", in the sense in which it is used herein, is defined as a web, web or wet laid sheet constituted by fibers containing cellulose. In this broad sense, these structures have a basis weight ranging from 10 g / m2 to approximately 1 kg / m and have densities ranging from approximately 0.1 g / cc to 1 g / cc. The cellulosic structures of the present invention preferably derive at least a portion of their strength from the ¿^ ^ ¿..Áa ^^. It is a natural fiber to fiber bonds that are formed when a web of short cellulosic fibers is drained and dried from an aqueous pulp. Accordingly, the so-called wet-laid papermaking is the most common process employing the present invention. The softening compositions of the present invention have a desirable low viscosity at room temperature that allows dilution as part of the papermaking process without the complexity and added cost of a heating step. The term "vehicle", in the sense in which it is used herein, means a fluid that completely dissolves a chemical paper additive, or a fluid that is used to emulsify a chemical paper additive or a fluid that is used to suspend a chemical papermaking additive. The vehicle can also serve as a carrier containing a chemical additive or aid in the release of a chemical papermaking additive. All references are intended to be indistinct and not limiting. Dispersion is the fluid that contains the chemical papermaking additive. The term "dispersion", in the sense in which it is used herein, includes pure solutions, suspensions and emulsions. For the purposes of this invention, all terms are indistinct and not imitative. The amount of the softening composition added to the cellulosic structure is preferably between about 0.05% and 10%, based on the total weight of the softening composition compared to the total weight of the resulting cellulosic structure. The cellulosic structure is preferably a tissue paper, more preferably a tissue paper having a basis weight of between about 10 and 100 g / m2 and a fiber density of less than about 0.6 g / cc. All percentages, ratios and proportions herein are presented by weight, unless otherwise specified.

BRIEF DESCRIPTION OF THE DRAWINGS While the specification concludes with the claims that are particularly directed and clearly claim the present invention, it is believed that the present invention will be better understood from the following description together with the attached example and with the following drawings, wherein the like reference numbers identify identical elements and wherein: Figure 1 is a schematic representation illustrating a creping paper process of the present invention for producing a soft and resistant tissue paper comprising papermaking fibers using the softening composition of the present invention. Figure 2 is a schematic representation illustrating the steps for the preparation of an aqueous paper pulp for a process for creped paper manufacture, according to one embodiment of the present invention. The present invention is described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION Briefly, the present invention provides a composition useful for softening cellulosic structures. Preferably, it is added to the final wetting process of a process for the manufacture of the cellulosic structure. More preferably, the cellulosic structure is a tissue paper. The resulting tissue paper comprising the composition of the present invention has a 'a ** JMAfeaai ", a softness that can be perceived by touch, improved.The softening composition is described, a method to produce the combination and a method to add it to the final wetting process of a papermaking process. The composition of the present invention is a dispersion of a softening active ingredient in a vehicle Importantly, the composition also comprises a bilayer breaking agent which .0 allows the composition to have a particularly high level of effective ingredient to soften the tissue paper webs and, at the same time, have a low viscosity at room temperature. These compositions are particularly desirable for the addition to the final process of wetting the papermaking process in order to provide paper using this process with desirable softness. These compositions are especially desirable for use in the processes used to provide 20 tissue products used for personal cleaning.

Tissue Paper The present invention is applicable to tissue paper in general, including but not limited to: ^ ^ ^ .- A ^ a ^ a conventionally pressed felt tissue paper; densified tissue paper with pattern such as that used by Sanford-Sisson and his progeny; and high volume, non-compact tissue paper such as exemplified by Salvucci. The tissue paper may be of a homogeneous or multilayer construction; and the tissue paper products produced therefrom can be of a single sheet or multiple sheet construction. The tissue paper preferably has a basis weight of between about 10 g / m2 and 100 g / m2 and a density of about 0.60 g / cc or less.Preferably, the basis weight will be between about 10 g / m2 and 80 g / m2, and the density will be 0.30 g / cc or less.Most preferably, the density will be between about 0.04 g / cc and 0.20 g / cc Conventionally pressed tissue paper and methods for making the same are known in the art. This paper is typically produced by depositing a paper pulp on a foraminous forming mesh This forming mesh is often referred to in the art as Fourdrinier mesh.After the pulp is deposited on the forming mesh, it is referred to as a web. In general, the water is removed from the web by vacuum, by mechanical and thermal pressing means, the web is drained by pressing it and drying it at an elevated temperature. The process described above is well known to those skilled in the art. In a typical process, a pulp paste of low consistency is provided in a pressurized head. The head has an opening for supplying a thin deposit of pulp paste on the Fourdrinier mesh to form a wet web. The web is then typically drained to a fiber consistency of between about 7% and 45% (total basis weight of the web) by vacuum draining and further dried by pressing operations wherein the web is subjected to pressure developed by members. mechanical in opposition, for example, cylindrical rollers. The drained web is then pressed further and dried by a current drum apparatus known in the art as a Yankee dryer. The pressure can be developed in the Yankee dryer by mechanical means such as an opposing cylindrical drum pressing against the weft. Multiple Yankee drums can be used, whereby an additional pressure is optionally placed between the drums. The tissue paper structures that are formed are referred to hereinafter as conventional pressed tissue paper structures. It is considered that these sheets will be compacted, since the weave is subjected to substantially total mechanical compression forces while the fibers are wetted and then dried in a compressed state. The resulting structure is strong and in general of a singular density, although it has very low volume, absorbency and softness. Patterned densified tissue paper is characterized by having a relatively high volumetric frame of relatively low fiber density and an array of densified areas of relatively high fiber density. The high volumetric plot is alternatively characterized as a frame of support regions. The densified zones are alternatively referred to as knuckle regions. The densified zones may be discretely separated within the high bulk frame or they may be interconnected, either completely or partially, within the high bulk frame. Preferred processes for manufacturing patterned densified tissue webs are described in U.S. Patent 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent 3,974,025, issued to Ayers on August 10, 1976; and United States Patents 4,191,609 and 4,637,859, issued to Trokhan on March 5, 1980, and January 20, 1987, respectively; the descriptions of each of them are incorporated herein by reference. In general, densified patterns with a preferred pattern are prepared by depositing a 10 paper stock on a foramed forming mesh such as, for example, a Fourdrmier mesh to form a wet weft and then juxtapose the weft against an array of supports as it is transferred from the formed mesh to a 15 structure comprising these supports for additional drying. The plot is pressed against the arrangement of supports, resulting in areas densified in the plot in the locations geographically corresponding to the points of 20 contact between the arrangement of supports and the wet screen. The rest of the frame that is not compressed during this operation is called a high volume frame. This high volume frame can be further discharged by means of the 25 application of fluid pressure, as for example * ~ j? *** a? * ** with a vacuum-type device or a blow-dryer or by mechanically pressing the screen against the support arrangement. The web is drained and optionally pre-dried, in such a way that compression of the high-volume web is substantially avoided. Preferably, this is carried out by fluid pressure, such as with a vacuum type device or a blow dryer, or alternatively by mechanically pressing the web against an array of supports, wherein the high bulk frame is not compress The draining, optional predrying and formation of the densified zones operations can be integrated or partially integrated to reduce the total number of processing steps performed. After the formation of the densified zones, the draining and the optional predrying, the weft is dried for its completion, preferably still avoiding the mechanical pressure. Preferably, between about 8% and 65% of the tissue paper surface comprises densified knuckles, the knuckles preferably have a relative density of at least 125% of the density of the high bulk frame.

The structure comprising a support arrangement is preferably a printing carrier fabric having a knuckle pattern shift that functions as the array of supports that facilitates the formation of the knuckles. densified zones at the time of pressure application. The knuckle pattern constitutes the support arrangement mentioned previously. Printing carrier fabrics are disclosed in U.S. Patent 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent 3,821,068, issued to Salvucci, Jr. et al. on May 21, 1974, U.S. Patent 3,974,025, issued to Ayers on August 10, 1976, U.S. Patent 3,573,164, issued to Friedberg, et al. on March 30, 1971, U.S. Patent 3,473,576, issued to Amneus on October 21, 1969, U.S. Patent 4,239,065, issued to Trokhan on December 16, 1980 and U.S. Patent 4,528,239 , granted to Trokhan on July 9, 1985, the exhibition of each of them is incorporated herein by reference. Preferably, the paste is first formed in a wet web on a forming carrier web t ésg3? = S-tfe. foraminada, such as a Fourdrinier mesh. The screen is drained and transferred to a printing fabric. The pulp can alternatively be initially deposited on a foraminous carrier carrier which also functions as a printing fabric. Once formed, the wet web is drained and preferably thermally pre-dried to a selected fiber consistency of between about 40% and 80%. The draining preferably is done with suction boxes or other vacuum devices, with blow dryers or combinations thereof. The print of the knuckles of the printing fabric is printed on the weft as previously discussed, before drying the weft for completion. One method to accomplish this is through the application of mechanical pressure. This can be done, for example, by pressing a contact point roller that supports the printing fabric against the face of a dryer drum, such as a Yankee dryer, where the web is placed between the contact point roller and the dryer drum. Preferably, the weft is also molded against the recording fabric before the drying is finished by applying fluid pressure with a vacuum device such as a suction box or ^ &J & ^ ^ ^ with a blow dryer. The fluid pressure can be applied to induce the printing of densified zones during the initial draining in a separate subsequent process step or a combination thereof. Patterned and unpacked densified tissue paper structures are described in U.S. Patent 3,812,000 issued to Joseph L. Salvucci, Jr. and Peter N. Yiannos on May 21, 1974 and U.S. Patent 4,208,459, granted to Henry E. Becker, Aibert L. McConnell and Richard Schutte on June 17, 1980, both of which are incorporated herein by reference. In general, densified and unpacked densified tissue paper structures are prepared by depositing a stock on a foraminated forming mesh such as a Fourdrinier mesh to form a wet weft, draining the weft and removing the additional water without mechanical compression. until the plot has a fiber consistency of at least 80% and creping the plot. The water is removed from the weft by vacuum draining and thermal drying. The resulting structure is a soft but high weak volume sheet of relatively uncompacted fibers. The binder material zátTáááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááááÉ The softening composition of the present invention may also be useful for softening uncolored tissue paper. Uncreped tissue paper, a term as used herein, refers to tissue paper that is dried without compression, more preferably by drying by passage of air. The resulting air-dried slits are patterned in such a way that the relatively high density areas are dispersed within a high bulk frame, including patterned densified tissue where the relatively high density areas are continuous and the plot high volume is discrete. To produce uncoated tissue paper webs, an embryonic web is transferred from the foraminous forming carrier at the time it is laid, to a carrier carrier of high fiber support, with slower movement. The web is then transferred to a drying cloth at the time it dries to a final dryness. These webs may offer some advantages in surface smoothness compared to creped paper webs.

Techniques for producing tissue without creping in this manner are shown in the prior art. For example, Wendt, et al. in U.S. Patent 5,672,248, issued September 30, 1997 and incorporated herein by reference, shows a method for making soft tissue products without creping. In another case, Hyland, et al. in European Patent Application 0 617 164 Al, published on September 28, 1994 and incorporated herein by reference, shows a method for manufacturing dried sheets by air passage without drying, smooth. Finally, Farrington, et al., In U.S. Patent 5,656,132 published August 12, 1997, the disclosure of each of them is incorporated herein by reference, describes the use of a tissue paper making machine. dried by soft air passage without the use of a Yankee.

Pulp Fibers The papermaking fibers used for the present invention usually include fibers derived from wood pulp. Other fibers of cellulosic fibrous pulp such as, for example, cotton linters, bagasse, etc., can be used and are intended to be within the scope of the invention. Synthetic fibers, such as for example rayon, polyethylene and polypropylene fibers can also be used in combination with natural cellulosic fibers. A polyethylene fiber which can be used is Pulpex®, available from Hercules, Inc. (Wilmington, DE). Applicable wood pulps include chemical pulps, such as, for example, Kraft, sulphite and sulfate pulps, as well as mechanical pulps including, for example, crushed wood, thermomechanical pulp and chemically modified thermomechanical pulp. However, chemical pulps are preferred since they impart a better feeling of softness to the tissue sheets produced therefrom. Pulps derived from both deciduous trees (hereinafter also referred to as "hardwood") and conifers ("hereinafter also referred to as" softwood ") can also be used. [Fibras También] Fibers can also be applied to the present invention. derived from recycled paper, which may contain any or all of the above categories as well as other non-fibrous materials such as, for example, fillers and adhesives used to facilitate the manufacture of original paper. Particularly preferred cellulosic pulps include long fibers such as, for example, Northern Kraft wood (NSK); short fibers, such as, for example, Eucalyptus; and secondary fibers such as, for example, white accounting papers before and after used, provision of coated books and office trash. These fibers can also be used in any desired combination with or without layering.

Smoothing Composition In general, the softening composition of the present invention comprises a dispersion of a softening active ingredient in a vehicle. When dispersed in a pulp used to produce tissue paper or other cellulosic structures as described herein, these compositions are effective in softening the structures. Preferably, the softening composition of the present invention has properties (eg, ingredients, rheology, pH, etc.) that allow easy application thereof on a commercial scale.

It is well known to those skilled in the art that quaternary ammonium compounds comprising the preferred active ingredient of the softening composition of the present invention therefore Generally, they are not easily dispersible in water. Preferred quaternary ammonium compounds are solids at room temperature and when added to water are difficult to disperse in a uniform dispersion even with the application of mechanical action. It is also known that the desired form of the softening composition is a liquid dispersible in cold water. Previous attempts to resolve this conflict have not been completely satisfactory. One method has been to use highly active organic solvents capable of solubilizing the liquid of the quaternary ammonium compound at room temperature and making it dispersible in water. For example, an alcohol with ba or molecular weight such as isopropanol can be used. These methods are not desirable due to the increased safety of the process and what is related to the environmental obligation (VOC) arising from the volatility of these solvents. Solvents that are less active may be used, although very high amounts are required aa-large that result in negative cost and environmental consequences. Making the quaternary ammonium compound more fluid is another method methodically employed, for example, by introducing more carbon-to-carbon double bonds into the long alkyl chains of the preferred ammonium compounds. These materials are typically either more expensive or are accompanied by side effects such as odor. The quaternary ammonium compounds can also be made more fluid and more dispersible by increasing their hydrophilicity, for example, by ethoxylating the alkyl chains thereof. This method decreases the effectiveness of the quaternary ammonium compound as a softening ingredient and also involves an additional processing cost. The composition of the present invention is in a fairly concentrated form of a preferred softening active ingredient, a quaternary ammonium compound, which is even readily dispersible in water. The following discusses each of the components of the softening composition of the present invention, the properties of the ^^ gÜ ^^^ composition, the methods to produce the composition and the methods to apply it.

Components Active Ingredients Softening The quaternary compounds have the formula: R?) 4-m-N + - [R2] mX " where: m e s 1 to 3; each Ri is an alkyl group of Ci-Cß, a hydroxyalkyl group, a hydrocarbyl group or substituted by hydrocarbyl, an alkoxylated group, a benzyl group or mixtures thereof; each R2 is a C ?4-C22 alkyl group, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof; and X "is any anion compatible with the softener are suitable for use in the present invention Preferably, each Rx is methyl and X" is chloride or methyl sulfate. Preferably, each R2 ^^ Jß | £ ja £ áag is linear or branched alkyl or alkenyl of Ciß-Ciß most preferably, each R2 is straight chain alkyl or alkenyl. Optionally, the substituent R2 can also be derived from vegetable oil sources. The various types of vegetable oils (for example, olive, cane, safflower, sunflower, etc.) can be used as sources of fatty acids to synthesize the quaternary ammonium compound. Branched chain active agents (e.g., as can be derived from the equivalent branched chain fatty acid) are also effective and have the additional advantage of being resistant to oxidation. Suitable branched-chain fatty acids which may serve as a starting point for these quaternary ammonium compounds include: 2-n-heptylundecanoic acid, 2-n-but-iloctanoic acid, 5,7,9-trimethylamnonanoic acid, acid 3, 5, 7, 9-t ethano-ilnonanoic acid, fa-heptyldecanoic acid and isostearic acid with the isostearic acid which is particularly preferred. These structures include the well-known dialkyldimethylammonium salts (eg, ditallowdimethylammonium chloride, ditallowdimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, etc.), in which Rx are methyl groups, R2 are tallow varying levels of saturation and X "is chloride or methyl sulfate, as discussed in Swern, Ed. in Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), tallow is a material that occurs naturally and has a variable composition. Table 6.13 in the reference identified in the above, edited by Swern, indicates that, typically, 78% or more of the tallow fatty acids contain 16 or 18 carbon atoms. Typically, half of the fatty acids present in sebum are unsaturated, mainly in the form of oleic acid. Synthetic "sebs" as well as natural ones are within the scope of the present invention. It is also known that depending on the characteristic requirements of the product, the level of saturation of the design can be made from non-hydrogenated products (soft) to the touch hydrogenated (partially hydrogenated) or completely hydrogenated (hard). All saturation levels described above are expressly intended to be included within the scope of the present invention. Particularly preferred variants of these wettable active ingredients are those which are considered to be mono or diester variations of these quaternary ammonium compounds having the formula: (R?) 4-m-N + - [(CH2) nY-R3] m? - where Y is -0- (0) C-, or -C (0) -0-, or -NH-C ( O) -, or -C (O) -NH-; : m is 1 to 3; n e s 0 to 4; each Ri is an alkyl group of C? -C6, a hydroxyalguyl group, a hydrocarbyl group or substituted with hydrocarbyl, an alkoxylated group, a benzyl group or mixtures thereof; each R3 is a linear or branched alkyl group of C] 3-C2 ?, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof; Y X "is any anion compatible with the softener, preferably Y = -0- (0) C, or -C (0) -0-; m = 2; and n = 2. Each substituent Ri is preferably a alkyl group of C? -C3, with methyl being the most preferred, Preferably, each R3 is C? 3-C? 7 alkyl and / or alkenyl, more preferably R3 is C? 5 alkyl and / or alkenyl. Straight-chain C, C 5-C 7 alkyl, most preferably each R 3 is straight chain C 7 alkyl, Optionally, the R 3 substituent can be derived from vegetable oil sources. Vegetable oils (eg, olive, sugarcane, safflower, sunflower, etc.) can be used as sources of fatty acids to synthesize the quaternary ammonium compound.Preferably, olive oils, cañola, safflower oils with high Oleic content and / or rape seed oils with high erucic content are used to synthesize the quaternary ammonium compound.As mentioned in the above, X "can be any anion compatible with the softener, for example, acetate, chloride, bromide, methyl sulfate, formate, sulfate, nitrate and the like may also be used in the present invention. Preferably X "is chloride or methyl sulfate.

Specific examples of quaternary ammonium compounds with ester functional group having the structures named above and suitable for use in the present invention include the well-known dialdimethyl ammonium diester salts such as diester dimethyl ammonium chloride, monoester chloride dimethyl ammonium dichloromethane dimethyl ammonium diester methylsulfate, dimethyl disodium methyl sulfate Ammonium dichloride (hydrogenated) dimethyl ammonium chloride and mixtures thereof. Diester dimethyl ammonium chloride and ditallow (hydrogenated) dimethyl ammonium diester chloride are particularly preferred. Diester dimethyl diester chloride Ammonium and ditallow (hydrogenated) dimethyl ammonium chloride are commercially available from Witco Chemical Company Inc. of Dublin, OH under the tradename ADOGEN SDMC. As mentioned in the above, typically 20 half of the fatty acids present in sebum are unsaturated, mainly in the form of oleic acid. Synthetic "sebs" as well as natural ones are within the scope of the present invention. It is also known that depending on the 25 characteristic requirements of the product, the degree of saturation of these tallow can be made from non-hydrogenated products (soft), to partially hydrogenated (to the touch), or completely hydrogenated (hard). All levels of saturation described in the foregoing are expressly intended to be included within the scope of the present invention. At least a minimum level of hydrogenation is preferred to eliminate, in particular, multiple unsaturated species (eg, linolenic derivatives) that are known to be more susceptible to oxidation resulting in rancidity. It should be understood that the substituents Ri, R and R3 can optionally be substituted with various groups such as alkoxy, hydroxyl or they can be branched. As mentioned in the above, preferably each Ri is methyl or hydroxyethyl. Preferably, each R 2 is C 2-Cig aland / or alkenyl, more preferably each R 2 is straight chain C 6 -C 8 alkenyl and / or alkenyl, most preferably each R 2 is alor alkenyl of C? 8 of straight chain. Preferably, R3 is C ?3-C17 aland / or alkenyl, more preferably R3 is straight chain C15-C? 7 aland / or alkenyl. Preferably X "is chloride or methyl sulfate.

In addition, the quaternary ammonium compounds with ester functional group can optionally contain up to about 10% mono (long chain al derivatives, for example: (R?) 2 -N + - ((CH2) 2OH) ((CH2) 20C (0) R3) X- as minor ingredients. These minor ingredients can act as emulsifiers and are useful in the present invention. Other types of quaternary ammonium compounds suitable for use in the present invention are described in U.S. Patent 5,543,067, issued to Phan et al. on August 6, 1996; U.S. Patent 5,538,595, issued to Trokhan et al., July 23, 1996; U.S. Patent 5,510,000, issued to Phan et al. on April 23, 1996; U.S. Patent 5,415,737, issued to Phan et al., May 16, 1995; and European Patent Application No. 0 688 901 A2, assigned to Kimberly-Clark Corporation, published on December 12, 1995; the descriptions of each of them are incorporated herein by reference.

The di-cuat variations of the quaternary ammonium compounds having an ester functional group can also be used and are intended to be within the scope of the present invention. These compounds have the formula: O (Rl) 2 (Rl) 2 or R1-C-O- (CH2) 2- + - (CH2) n -N + (CH2) 2 - O -C -R3 2 X " In the structure named above, each Ri is an alor hydroxyalgroup of Ci-Ce, R3 is a hydrocarbyl group of Cn-C2 ?, n is from 2 to 4 and X "is a suitable anion, such as for example , a halide (for example, chloride or bromide) or methyl sulfate, preferably, each R3 is aland / or alkenyl of C? 3-C? - >; most preferably each R3 is straight chain Ci5-C17 alkyl and / or alkenyl and Ri is a methyl. Parenthetically, insofar as it is not intended to be limited by theory, it is believed that the ester entity or entities of the aforementioned quaternary ammonium compounds provide a measure of biodegradability for these compounds. Importantly, the quaternary ammonium compounds with ester functional group used herein are t ag- ^ - a ^^ biodegrade more rapidly than conventional dialkyl dimethyl ammonium chemical softeners. The use of quaternary ammonium ingredients as described hereinbefore is carried out more efficiently if the quaternary ammonium ingredient is accompanied by a suitable plasticizer. The term "plasticizer," in the sense in which it is used herein, refers to an ingredient capable of reducing the melting point and viscosity at a given temperature of a quaternary ammonium ingredient. The plasticizer can be added during the quaternization step in the manufacture of the quaternary ammonium ingredient or it can be added after quaternization but before application as a softening active ingredient. The plasticizer is characterized as being practically inert during the chemical synthesis of the quaternary ammonium compound where it can act as a viscosity reducer to aid in the synthesis. Preferred plasticizers are non-volatile polyhydroxy compounds. Preferred polyhydroxy compounds include glycerol and polyethylene glycols having a molecular weight of between about 200 and 2000, with polyethylene glycol having a molecular weight of between -atStoí.B ^^^ * ^ approximately 200 and 600 which is particularly preferred. When these plasticizers are added during the manufacture of the quaternary ammonium ingredient, they comprise between about 5% and 75% of the product of that manufacture. Particularly preferred mixtures comprise between about 15% and 50% propellant piles.

Vehicle In the sense in which it is used herein, a "vehicle" is used to dilute the active ingredients of the compositions described herein that form the dispersion of the present invention. A vehicle can dissolve these components (pure solution or micellar solution) or these components can be distributed throughout the vehicle (dispersion, emulsion or spongy phase). The vehicle of a suspension or emulsion is typically the continuous phase thereof. That is, other components of the dispersion or emulsion are dispersed on a particular level or as discrete particles or molecular aggregates throughout the vehicle.

For the purposes of the present invention, one purpose for which the vehicle serves is to dilute the concentration of the softening active ingredients in such a way that these ingredients can be applied efficiently and economically. These diluted compositions are more easily diluted to use the concentration without the need for complex processing equipment. The vehicles and softening compositions comprising these vehicles have also been found to be particularly useful in facilitating the incorporation of the softening active ingredients into the tissue webs on a commercial scale. While the softening ingredients can be dissolved in a vehicle that forms a solution therein, materials that are useful as solvents for the suitable softening active ingredients are not commercially desirable for safety and environmental reasons. Therefore, to be suitable for use in the vehicle for the purposes of the present invention, a material must be compatible with the softening active ingredients described herein and with the tissue substrate with which the softener compositions of the invention will be used. present invention.

In addition, having none of the ingredients that will have consequences in terms of safety (either in the tissue manufacturing process or to the users of the tissue products) are used. softening compositions described herein) and not creating an unacceptable risk to the environment Suitable materials for the vehicle of the present invention include liquids with hydroxyl functional group more preferably water.

Electro] ito While water is a particularly preferred material for use in the vehicle of the present invention, water alone is not preferred as a vehicle. Specifically, when the softening active ingredients of the present invention are dispersed in water at a level suitable for application to a tissue web, the dispersion has an unacceptably high viscosity. While not intended to be limited by theory, it is believed that the combination of water and the softening active ingredients of the present invention to form these dispersions creates a liquid crystalline phase having a high viscosity. Compositions having this high viscosity are difficult to dilute for use in a process for producing tissue webs that soften the web. It has been found that the viscosity of the dispersions of the softening active ingredients in the water can be substantially reduced, while maintaining a desirable high level of the softening active in the softening composition by the simple addition of a suitable electrolyte to the vehicle. Again, without pretending to be limited by theory, it is believed that the electrolyte protects the electrical charge around the bilayers and vesicles, reducing interactions and decreasing resistance to movement resulting in a reduction in system viscosity. Additionally, again without being limited by theory, the electrolyte can create a difference of osmotic pressure through the vesicular walls that could tend to extract water from the interior through the vesicular wall reducing the size of the vesicles and providing more water "free", resulting again in a decrease in viscosity. Any electrolyte that meets the general criteria described in the above for the ^ jOfJ ^^ z. ^., ...

Suitable materials for use in the vehicle of the present invention and which is effective in reducing the viscosity of a dispersion of a softening active ingredient in water is suitable for use in the vehicle of the present invention. In particular, any of the known water soluble electrolytes that meet the above criteria can be included in the vehicle of the softening composition of the present invention. When present, the electrolyte can be used in amounts up to 25% by weight of the softening composition, but preferably not greater than about 15% by weight of the softening composition. Preferably, the electrolyte level is between about 0.1% and 10% by weight of the softening composition based on the anhydrous weight of the electrolyte. Even more preferably, the electrolyte is used at a level between about 0.3% and 1.0% by weight of the softening composition. The minimum amount of the electrolyte will be that amount sufficient to provide the desired viscosity. The dispersions typically exhibit a non-Newtonian rheology and are shear thinning with a general desired viscosity ranging from g & g ^ ¿gAa'-j- -approximately 10 centipoise (cp) to about 1000 cp, preferably in the range between about 10 and 200 cp, as measured at 25 ° C and at a shear rate of 100 sec "1 using the method described in the section on TEST METHODS below .. Suitable electrolytes include halide, nitrate, nitrite and sulfate salts of alkali or alkaline earth metals, as well as the corresponding ammonium salts Other useful electrolytes include salts alkaline and alkaline inotreases of simple organic acids such as for example sodium formate and sodium acetate, as well as the corresponding ammonium salts.The preferred electrolytes include the sodium chloride, calcium and magnesium salts.Calcium chloride is an electrolyte particularly preferred for the softening composition of the present invention. While not intended to be limited by theory, it is believed that the nature of the The presence of the calcium ion makes it particularly effective in reducing the viscosity of the vesicular dispersion of the softening active ingredient. If desired, compatible mixtures of various electrolytes are also suitable.

Bilayer Breaking Agent A bilayer breaking agent is an essential component of the invention. While, as shown above, the vehicle, particularly the electrolyte component dissolved therein, performs an essential function in the preparation of the cellulosic structures of the present invention, it is desirable to also maximize the concentration of the softening active ingredient. as long as an acceptable viscosity is maintained. As noted above, the addition of the electrolyte allows an increase in the concentration of the softening active ingredient in the softening composition without unduly increasing the viscosity. However, if too much electrolyte is used, a phase separation may occur. It has been found that adding a bi-layer breaking agent to the softening composition allows more softening active ingredient to be incorporated therein while maintaining a viscosity at an acceptable level. As used herein, a "bi-layer breaking agent" is an organic material which, when mixed with a dispersion of a softening active ingredient in a vehicle, is compatible with ts at least one of the softening active ingredients and causes a reduction in the viscosity of the dispersion. Without being limited by theory, it is believed that the bilayer breaking agents function by penetrating the palisade layer of the liquid crystalline structure of the dispersion of the softening active ingredient in the carrier and breaking the order of the liquid crystalline structure. It is believed that this breakdown reduces interfacial tension at the hydrophobic water interface, thus promoting flexibility with a resultant reduction in viscosity. In the sense in which it is used herein, the term "palisade layer" is intended to describe the area between the hydrophilic groups and the first few carbon atoms in the hydrophobic layer (M. J Rosen, Surfactants and interfacial phenomena, Second Edition, pages 125 and 126). In addition to providing the viscosity reduction benefits discussed above, materials suitable for use as a bi-layer breaking agent must be compatible with other components of the softening composition. For example, a suitable material should not react with other components of the softening composition for < BA > fa **** ', ri cause the softening composition to lose its softening capacity. The bilayer breaking agents useful in the compositions of the present invention are preferably surfactant materials. These materials comprise both hydrophobic and hydrophilic entities. A preferred hydrophilic entity is a polyalkoxylated group, preferably a polyethoxylated group. These preferred materials are used at a level of between about 1% and 15% of the level of the softening active ingredient. Preferably, the bi-layer breaking agent is present at a level between about 2% and 10% of the level of the softening active ingredient. Particularly preferred bilayer cleaving agents are nonionic surfactants derived from amine, amide, fatty alcohol with amine oxide, fatty acid, alkyl phenol, and / or primary and / or secondary alkyl aryl carboxylic acid compounds, saturated and / or unsaturated. saturate, each preferably have between about 6 and 22, more preferably between about 8 and 18 carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene chain, wherein at least one active hydrogen of the E, í¿a¿s *.? * T. «'^. ^ riS- :. The compounds are ethoxylated with < 50, preferably < 30, more preferably between about 3 and 15, and even more preferably between about 5 and 12, ethylene oxide entities to provide an HLB of between about 6 and 20, most preferably between about 8 and 18 and most preferably between about 10 and 15. Suitable bilayer cleaving agents also include nonionic surfactants with bulky major groups selected from: a. surfactants that have the formula R1-C (0) -Y '- [C (R5)] m-CH20 (R20) ZH wherein R1 is selected from the group consisting of alkyl or saturated or unsaturated, primary, secondary or branched alkyl aryl hydrocarbons; the hydrocarbon chain has a length of between about 6 and 22; Y 'is selected from the following groups: -0 -; -N (A) -; and mixtures thereof; and A is selected from the following groups: H; R1; - (R2-0) z-H; - (CH2) XCH3; phenyl or substituted aryl, wherein 0 < x < about 3 and z is between about 5 and 30; each R2 is selected from the following groups or combinations of the following groups: - (CH2) n ~ and / or - [CH (CH3) CH2] -; and each R5 is selected from the following groups: -OH; and -0 (R20) z-H; and m is between about 2 and 4; b. surfactants that have the formulas: where Y "= N or O; and each R5 is independently selected from the following: -H, -OH, - (CH2) XCH3, -0 (OR2) zH, -OR1, -OCYOJR1, and -CH (CH. 2- (OR2) Z-H) -CH2- (OR2) Z, -C (O) R1, x and R1 are as defined above and 5 <z, z 'and z "< 20, most preferably 5 < z + z '+ z "= 20, and most preferably, the heterocyclic ring is a five-membered ring with Y" = O, one R5 is -H, two R5 are -0- (RO) zH and at least one R5 has the following structure -CH (CH2- (OR2) Z "-H) -CH2- (OR2) z. -C (O) R1 with 8 < z + z '+ z "< 20 and R1 is a hydrocarbon with 8 to 20 carbon atoms and not an aryl group: c) polyhydroxy fatty acid amide surfactants of the formula: , more than J ^ ^ M ^ R2-C (O) -N (R1) -Z wherein: each R 1 is H, C 1 -C 4 hydrocarbyl, C 1 -C 4 alkoxyalkyl or hydroxyalkyl; and R2 is a C5-C31 hydrocarbyl entity; and each Z is a polyhydroxyhydrocarbyl entity having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain or an ethoxylated derivative thereof; and each R 'is H or a cyclic mono- or poly-saccharide, or an alkoxylated derivative thereof; and Suitable phase stabilizers also include surfactant complexes formed by a surfactant ion which is neutralized with the opposite charge surfactant ion or an electrolyte ion which is suitable for reducing the dilution viscosity. Examples of representative bilayer breaking agents include: (1) Alkoxylated non-ionic surfactants of alkyl or of Iqui 1-aryl Suitable alkoxylated nonionic alkyl surfactants are generally derived from primary and secondary saturated or unsaturated alcohols, fatty acids, alkyl phenols or alkyl aryl acid carboxylic (eg, benzoic), wherein the hydrogen or active hydrogens are alkoxylated with < about 30 alkylene oxide entities, preferably ethylene, (eg, ethylene oxide and / or propylene oxide). These nonionic surfactants for use herein preferably have between about 6 and 22 carbon atoms on the alkyl or alkenyl chain and are in a straight chain configuration, preferably straight chain configurations having between about 8 and 18 carbon atoms, with the alkylene oxide being present, preferably in the primary position, in average amounts of < about 30 moles of alkylene oxide per alkyl chain, more preferably between about 3 and 15 moles of alkylene oxide and most preferably between about 6 and 12 moles of alkylene oxide. Preferred materials of this class also have a thawing temperature of less than about 70 ° F (21 ° C) and / or do not solidify in these softening compositions. Examples of alkoxylated alkyl surfactants with straight chains include Neodol® 91-8, 23-5, 25-9, 1-9, 25-12, 1-9 and 45-13 of Shell, Plurafac® B-26 and C- 17 of BASF, and Brij® 76 and 35 of ICI Surfactants. Examples of alkoxylated surfactants with alkyl-aplo include: Surfonic N-120 from Huntsman, Igepal® CO-620 and CO-710, from Rhone Poulenc, Triton® N-111 and N-150 from Union Carbide, Dowfax® 9N5 from Dow and Lutensol® AP9 and AP14, from BASF. (2) Non-ionic alkoxylated surfactants of amine oxide or alkyl or alkyl aryl amine Suitable non-ionic alkoxylated surfactants of alkyl with amino functional group are generally derived from primary and secondary fatty alcohols, saturated or unsaturated, fatty acids, methyl fatty esters, alkyl phenol, alkyl benzoates and alkyl benzoic acids which are converted to amines, amine oxides and optionally substituted with a second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains attached to the amine functional group who has each one < about 50 moles of alkylene oxide entities (eg, ethylene oxide and / or propylene oxide) per mole of amine. The amine, amide or amine oxide surfactants for use herein have between about 6 and 22 carbon atoms and are in a configuration of chain either straight or branched, preferably there is a hydrocarbon in a straight chain configuration having between about 8 and 18 carbon atoms with one or two alkylene oxide chains attached to the amine entity in average amounts of < About 50 moles of alkylene oxide per amine entity, more preferably between about 3 and 15 moles of alkylene oxide and most preferably a single alkylene oxide chain on the amine entity containing between about 6 and 12 moles of aniikylene oxide per amine entity. Preferred materials of this class also have thawing temperatures less than about 70 ° F (21 ° C) and / or do not solidify in these softening compositions. Examples of ethoxylated amine surfactants include Berol® 397 and 303 from Rhone Poulenc and Ethomeens® C / 20, C25, T / 25, S / 20, S / 25 and Ethodumeens® T / 20 and T25 from Akzo. Preferably, the compounds of alkoxylated alkyl or alkyl aryl surfactants and alkyl or alkyl aryl amine, amide and alkoxylated amine oxide have the following general formula: S ^^^^ - S wherein each R1 is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain or alkyl-aplo hydrocarbons; the hydrocarbon chain preferably has a length of between about 6 and 22, more preferably between about 8 and 18 carbon atoms, and even more preferably between 8 and 15 carbon atoms, preferably without a linear aryl entity; wherein each R2 is selected from the following groups or combinations of the following groups: - (CH2) n- and / or - [CH (CH3) CH2]; where approximate-ament e 1 < n < approximately 3; And it is selected from the following groups: -0-; -N (A) q-; -C (0) 0-; - (0 <r) N (A) q-; -B-R3-0-; -B-R3-N (A) q-; -B-R3-C (O) O-; -B-R3-N (-0) (A) -; and mixtures thereof; where A is selected from the following groups: H; R1; - (R2-0) z-H; - (CH2) XCH3; phenyl, or substituted aryl, wherein 0 < x < approximately 3 and B is selected from the following groups: -0-; -N (A) -; -C (0) 0-; and mixtures thereof in which A is as defined in the above; and wherein each R3 is selected from the following groups: R2; phenyl; or substituted aryl. The terminal hydrogen in each alkoxy chain can be faM-Jtatoa ^ -replace with a short chain of alkyl C or acyl group to "top off" the alkoxy chain. z is between about 5 and 30. p is the number of ethoxylate chains, typically one or two, preferably one and m is the number of hydrophobic chains, typically one or two, preferably one and q is a number that completes the structure, usually one. Preferred structures are those in which m = l, p = l or 2, and 5 < < 30 and q can be 1 or 0, although when p = 2, q must be 0; the most preferred are structures in which m = 1, p = 1 or 2, and 7 < < twenty; and even more preferred are the structures in which m = 1, p = 1 or 2, and 9 < < 12. The and preferred is 0. (3) Non-alkoxylated and non-alkoxylated nonionic surfactants with bulky main groups Suitable alkoxylated and non-alkoxylated bilayer cleaners with bulky main groups are generally derived from primary or secondary saturated or unsaturated fatty alcohols, fatty acids, alkyl phenol and alkyl benzoic acids which are derived with a carbohydrate group or a heterocyclic main group. This structure can be S = jte & ^ a. < & amp; > "- optionally substituted with more alkoxylated alkyl or alkylaryl or non-alkoxylated hydrocarbons The heterocyclic or carbohydrate is alkoxylated with one or more alkylene oxide chains (eg, ethylene oxide and / or propylene oxide) each having <50, preferably> about 30 moles per mole of heterocyclic or carbohydrate The hydrocarbon groups in the carbohydrate or the heterocyclic surfactant to be used in the 10 present have between about 6. and 22 carbon atoms and are in a straight chain configuration, preferably there is a hydrocarbon having from about 8 to 18 carbon atoms with one or two alkylene oxide chains 15 of carbohydrate or a heterocyclic entity with each alkylene oxide chain present in average amounts of < about 50, preferably < about 30 moles of carbohydrate or heterocyclic entity, more preferably between About 3 and 15 moles of alkylene oxide per alkylene oxide chain and more preferably between about 6 and 12 moles of total alkylene oxide per molecule of surfactant including alkylene oxide or both the chain of 25 hydrocarbon as the heterocyclic entity or ? «S & carbohydrate. Examples of bilayer cleaving agents of this class are Tween® 40, 60 and 80 available from ICI Surfactants. Preferably, the compounds of the alkoxylated and non-alkoxylated nonionic surfactants with bulky main groups have the following general formulas: R'-CtO) -Y '- [C (Rb)] ra-CH20 (R20) ZH wherein R1 is selected from the group consisting of saturated or unsaturated alkyl, primary or secondary, or branched chain, or alkylaryl hydrocarbons; the hydrocarbon chain has a length of between about 6 and 22; Y 'is selected from the following groups: -0-; -N (A) -; and mixtures thereof; and A is selected from the following groups: H; R1; - (R2-0) z-H; - (CH2) XCH3; phenyl or substituted aryl, wherein 0 < x < about 3 and z is between about 5 and 30; each R2 is selected from the following groups or combinations of the following groups: - (CH2) n- and / or - [CH (CH3) CH2] -; and each R is selected from the following groups: -OH; and -0 (R20) z-H; and m is between about 2 and 4; f hú ^^ f3"^^^^ - ^^ 1 Another general formula useful for this class of surfactants is where Y "= N or O, and each R is independently selected from the following: -H, -OH, - (CH2) XCH3, - (OR2) zH, -OR1, -OCYOJR1, and -CH2 (CH2- ( OR2) z-ri) -CH2- (OR2) Z'-C (O) R1, with x R1, and R2 as defined above in section D above and z, z 'and z "are all about 5 < a = about 20, most preferably the total number of z + z '+ z "is about 5 <to <20 about. In a particularly preferred form of this structure, the heterocyclic ring is a five-membered ring with Y 'O, an R3 is -H, two R5 are -0- (R20) zH and at least one R5 has the following structure -CH (CH2- (OR2) Z »-H) -CH2- (OR2) z- - < Z (0) RX with the total z + z '+ z "= to approximately 8 < a < about 20 and R1 is a hydrocarbon with between about 8 to 20 carbon atoms and without aryl group; üitt? íaÉttitfWtaKs ^ y ^ mm ^ - '.. ^ = fcfi ^ = teá j Another surfactant group that can be used is the polyhydroxy fatty acid amide surfactants of the formula.

R6-C (O) -N (R7) -W wherein: each R7 is H, C? -C hydrocarbyl, C? ~ C alkoxyalkyl or hydroxyalkyl, for example, 2-hydroxyethyl, 2-hydroxypropyl, etc., preferably C? preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (ie, methyl) or methoxyalkyl; and R6 is a C5-C3 hydrocarbyl entity, preferably straight chain C7-C19 alkyl or alkenyl, more preferably Cg-C alkyl or alkenyl? straight chain, most preferably straight chain C 11 -C 17 alkyl or alkenyl, or mixtures thereof; and is a polyhydroxyhydrocarbyl entity having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, it will be derived from a reducing sugar in a reductive amination reaction; most preferably W is a glycityl entity. Preferably, it will be selected from the group consisting of -CH2- (CHOH) n -CH2OH, -CH (CH2OH) - (CHOH) n-CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, where n is an integer from 3 to 5, inclusive, and R 'is H. or a cyclic mono- or poly-saccharide and alkoxylated derivatives thereof. The glycityls are most preferred, wherein n is 4, in particular -CH2- (CHOH) 4-CH20. Mixtures of the above W entities are desirable. R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl or N-2-hydroxypropyl. R6-C0-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. W may be 1-deoxyglucityl, 2-deoxy fructinyl, 1-deoxymalotyl, 1-deoxylactyl, 1-deoxygalactityl, 1-deoxyanilityl, 1-deoxy-thalothyl, etc. (4) Cationic alkoxylated quaternary ammonium surfactants Cationic, alkoxylated quaternary ammonium surfactants suitable for this invention are generally derived from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids and / or benzoate esters substituted with alkyl and / or acids which are converted to amines which optionally can be further reacted with another long chain alkyl or alkyl aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having < about 50 moles of alkylene oxide entities (eg, ethylene oxide and / or propylene oxide) per mole of amine. In this class, products obtained from the quaternization of primary, secondary or branched, saturated or unsaturated, aliphatic amines having one or two hydrocarbon chains of between 6 and 22 carbon atoms alkoxylated with one or two chains are typical. of alkylene oxide in the amine atom each having less than < about 50 alkylene oxide entities. The amine hydrocarbons for use herein have between about 6 and 22 carbon atoms and are in a straight chain or branched chain configuration, preferably there is an alkyl hydrocarbon group in a straight chain configuration having between about 8 and 18 carbon atoms.

Suitable quaternary ammonium surfactants are produced with one or two alkylene oxide chains attached to the amine entity, in average amounts of < about 50 moles of alkylene oxide per alkyl chain, more preferably between about 3 and 20 moles of alkylene oxide and most preferably between 5 and 12 moles of alkylene oxide per hydrophobic group, for example, alkyl. Preferred materials of this class also have thawing temperatures below about 70 ° F (21 ° C) and / or do not solidify in these softening compositions. Examples of suitable bilayer cleavage agents of this type include Ethoquad® 18/25, C / 25 and 0/25 Akzo and Variquat®-66 (tallow alkyl bis (polyoxyethy) ammonium ethyl sulfate with a total of about 16 ethoxi units) from Witco. Preferably, the compounds of the alkoxylated ammonium cationic surfactants have the following general formula: (R Y- [(R2-0) Z-H] p.}. + X " wherein R1 and R2 are as defined above in section D; | ^^ g¿8 ^ ¿fc .., A,. ^ a- ^ i¡ Y is selected from the following groups: = N + - (A) q; - (CH2) n-N + - (A) q; -B- (CH2) n "-N + - (A) 2; - (phenyl) -N + - (A) q; - (B-phenyl) -N + - (A) q; with n which is between about 1 and 4. Each A is independently selected from the following groups: H; R1; - (R20) zH; - (CH2) XCH3; phenyl and substituted aryl; wherein 0 <x <about 3; and B is selected from the following groups: -0-; -NA-; -NA2; -C (0) 0-; and -C (0) N (A) -; wherein R2 is defined as above, q = 1 or 2 and X "is an anion that is compatible with the softening active ingredient and other components of the softening composition. Preferred structures are those in which m = l, p = 1 or 2, and approximately 5 < < about 50, most preferred are structures in which m = l, p = 1 or 2 and approximately 7 < < approximately 20 and those with the highest preference are the structures in which m = 1, p = 1 or 2, approximately 9 < < approximately 12. (5) Nonionic surfactants alkoxylated with alkyl amide Suitable surfactants have the formula: R-C (0) -N (R4) n- [R1 ©) (R? 0), R3] wherein R is linear alkyl of C, -2, branched alkyl of C7-2, linear alkenyl of C-21, branched alkenyl of C7_2? and mixtures thereof. Preferably R is alkyl or linear alken of R1 is -CH2-CH2-, alkyl line of C3-C4, branched alkyl of C3-C4 and mixtures thereof; preferably R2 is -CH (CH3) -CH2-. The surfactants comprising a mixture of units "X and R2 preferably comprise between about 4 and 12 units of -CH2-CH2 in combination with between about 1 and 4 units of -CH (CII 3 ¡-CH? they may be alternating or they may be grouped together in any suitable combination for the formulator.Preferably, the ratio of units R1 to units R2 is between about 4: 1 and 8: 1. say, -C (CH3) H-CH2-) is attached to the nitrogen atom ^ &... followed by chain equilibrium comprising between about 4 and 8 units of -CH2-CH2-. R 3 is hydrogen, linear C 1 -C 4 alkyl, branched C 3 -C 4 alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen. R 4 is hydrogen, linear C 1 -C 4 alkyl, branched C 3 -C 4 alkyl and mixtures thereof; preferably hydrogen. When the index m is equal to 2, the index n must be equal to 0 and the unit R4 is absent. The index m is 1 or 2, the index n is 0 or 1, with the proviso that m + n equals 2; preferably m is equal to 1 and n is equal to 1, which results in a unit of - [(R1 ©) x (R20) and R3] and R4 which is present in the nitrogen. The index x is between 0 and 50, preferably between 3 and 25, more preferably between 3 and 10. The index y is between 0 and 10, preferably 0, however, when the index and is not equal to 0, and is from 1 to about 4. Preferably all alkylenoxy units are ethyleneoxy units. Examples of suitable ethoxylated alkyl amide surfactants are Rewopal® C6 from Witco, ^^^^ - ^ -: - "-. ^^« «tataBiBta ^ Amidox® C5 from Stepan and Ethomid® 0/17 and Ethomid® HT / 60 from Akzo.

Minor Components of the Softening Composition The vehicle may also comprise minor ingredients as would be known in the art. Examples include: mineral acids from buffer systems for pH adjustment (may be required to maintain hydrolytic stability for certain softening active ingredients) and antifoaming ingredients eg, a silicone emulsion such as is available from Dow Corning, Corp. of Midland, MI as Dow Corning 2310) as a processing aid to reduce foaming when using the softening composition of the present invention. Stabilizers can also be used to improve the uniformity and shelf life of the dispersion. For example, an ethoxylated polyester, HOE S 4060, available from Clariant Corporation of Charlotte, NC may be included for this purpose.

Formation of the Softening Composition As noted in the foregoing, the softening composition of the present invention is a * s * .t. , "^^. ^. ^. ^ - ^ - a dispersion of a softening active ingredient in a vehicle. Depending on the selected softening active ingredient, level and other desired application factors as might be required for a particular level of the softening active ingredient in the composition, the level of the softening active ingredient may vary from about 10% of the composition and 50% of the composition. Preferably, the softening active ingredient comprises between about 25% and 45% of the composition. More preferably, the softening active ingredient comprises between about 30% and 40% of the composition. The nonionic surfactant is present at a level of between about 1% and 15% of the softening active ingredient level, preferably between about 2% and 10%. Depending on the method used to produce the softening active ingredient, the softening composition may also comprise between about 2% and 30%, preferably between about 5% and 25% of a spicy pias. As noted in the above, the preferred primary component of the vehicle is water. In addition, the vehicle preferably comprises an alkaline or alkaline earth metal electrolyte and may comprise minor ingredients for adjusting the pH, for controlling the foam, or for aiding in the stability of the dispersion. The following describes the preparation of a particularly preferred softening composition of the present invention. A particularly preferred softening composition of the present invention (Composition 1) is prepared as follows. The materials are defined more specifically in the table detailing Composition 1 after this description. The quantities used in each step are sufficient to result in the finished composition detailed in that table. The appropriate amount of water is heated (an extra amount is added to compensate for the loss of evaporation) at approximately 165 ° F (75 ° C). Hydrochloric acid (25% solution) and antifoam ingredient are added. Concurrently, the mixture of the softening active ingredient, plasticizer, and non-ionic surfactant melts upon heating to a temperature of about 150 ° F (65 ° C). The molten mixture of the softening active ingredient, plasticizer and nonionic surfactant is then slowly added to the acidic aqueous phase heated with mixing to evenly distribute the dispersed phase throughout the vehicle. (The water solubility of polyethylene glycol probably goes to a continuous phase, although this is not essential for the invention and the plasticizers that are more hydrophobic and thus remain associated with the alkyl chains of the quaternary ammonium compound are also allowed to be within the scope of the present invention.) Once the softening active ingredient is completely dispersed, part of the calcium chloride is added (as a 2.5% solution) intermittently with mixing to provide an initial viscosity reduction. The plasticizer is then added slowly to the mixture with continuous stirring. Finally, the remainder of the calcium chloride (as a 25% solution) is added with continuous mixing. m * - * »** -. ^ * - Composition 1 Component Concentration Continuous Phase Water c.b.p. 100% Electrolyte1 0.6% Antifoam2 0.2% Bicapa Breakthrough Agent 3.5 1.0% Hydrochloric Acid 0.04% Plasticizer "19% Stabilizer 0.5% Phase Dispersed Active Ingredient Softener" 40.0% 0.38% calcium chloride aqueous solution 2. 5% and 0.22% aqueous solution of calcium chloride 25% 2. Silicone emulsion (active at 10%) - Dow Corning 2310®, marketed by Dow Corning Corp., Midland, MI Suitable nonionic surfactants are available from Shell Chemical of Houston, TX under the tradename NEODOL 91-8. Available as a 25% solution from J. T. Baker Chemical Company by Phil lipsburg, NJ asai ^ m & 5. The bilayer cracking agent, the plasticizer and the softening active ingredient are obtained pre-mixed from Witco Chemical Company of Dublin OH (approximately 2 parts of Neodol 91-8, approximately 29 parts of polyethylene glycol 400 and approximately 69 parts of tallow diester quaternary) 6. The stabilizer is HOE S 4060, from Clariant Corp., Charlotte, NC The resulting chemical softening composition is a milky, low viscosity dispersion suitable for application to cellulosic structures as will be described below to provide a soft touch desirable for these structures. A non-Newtonian viscosity of shear thinning is shown. Suitably, the composition has a viscosity of less than about 1000 centipoise (cp), as measured at 25 ° C and a shear rate of 100 sec "1 using the method described in the section on later TEST METHODS. Preferably, the composition has a viscosity less than about 500 cp, Most preferably, the viscosity is less than about 300 cp. ^^ ß? ¥ * > ^. The chemical composition is easily handled as a liquid and is easily transported from the point of manufacture to the point of use since it has a relatively high concentration of the active ingredient. At the point of use, it is advisable to dilute the concentrate at a concentration of use. This step of dilution is necessary to allow the proper measurement of the softening active ingredient in the papermaking process. That is, in a commercial papermaking process, a fairly large amount of a dispersion having a low concentration of this softening active ingredient is measured in a suitable process stream. It will be recognized that the concentration of use depends on various factors including: process capability for the measurement step, the desired increase in the softening active ingredient, the flow rates of the various process streams and other factors will be recognized by those who have experience in the technique. A suitable range of use concentrations has been found to be between about 0.5% and 10%, wherein the concentration is expressed as a percentage by weight of softening active ingredient. Preferably, the use concentration is between about 0.5% and 5%, more preferably between about 0.5% and 2%. A particularly preferred concentration of use is about 1%.

Optional Chemical Additives Other materials can be added to the aqueous paper pulp or embryonic web to impart other desirable characteristics to the product or to improve the papermaking process provided that they are compatible with the chemistry of the softening composition and do not significantly and adversely affect the softness or resistance character of the present invention. The following materials are expressly included, although their inclusion is not presented to be totally inclusive. Other materials may also be included with the proviso that they do not interfere or neutralize the advantages of the present invention. It is common to add a cationic charge-derived species to the papermaking process to control the zeta potential of the aqueous paper pulp as it is supplied for the papermaking process. These materials are used because most of the solids in nature have negative surface charges, including the surfaces of the fibers ^ £ | Ug cellulosic and fine and more inorganic fillers. A derivative species of cationic charge traditionally used is alum. More recently in the art, charge bypass is made by using cationic synthetic polymers of relatively low molecular weight which preferably have a molecular weight of not more than about 500,000 and more preferably not greater than about 200., 000, or even approximately 100,000. The charge densities of these low molecular weight cationic synthetic polymers are relatively high. These charge densities range from about 4 to 8 equivalent of cationic nitrogen per kilogram of polymer. One material, eg, is Cypro 514®, a product of Cytec, Inc. of Stamford. CT. The use of these materials is expressly left within the practice of the present invention. The use of microparticles of higher anionic charge, of high surface area, is shown in the art for the purpose of improving formation, drainage, strength and retention. See, for example, U.S. Patent 5,221,435, issued to Smith on June 22, 1993, the disclosure of which is incorporated herein.

¡SíaÉÉftmiS! : AS £ & ¿? ^ ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ as a reference. Common materials for this purpose are colloidal silica or bentonite clay. The incorporation of. These materials are expressly included within the scope of the present invention. If a permanent wet strength is desired, the group of chemicals, including polyamide-epichlorohydrin, polyacrylamides, styrene-butadiene networks, can be added to the pulp or embryonic web; polyvinyl alcohol without solubilizing; urea-formaldehyde; polyethyleneimine; chitosan polymers and mixtures thereof. Preferred resins are cationic wet strength resins, such as polyamide-epichlorohydrin resins. Suitable types of these resins are described in U.S. Patents 3,700,623, issued October 24, 1972 and 3,772,076, issued November 13, 1973, both to Keim, the disclosure of which is incorporated herein. as reference. A commercial source of useful polyamide-epichlorohydrin resins is Hercules, Inc. of Wilmington, Delaware, which markets this resin under the trademark Kymene 557H®. Many paper products must have limited resistance when wetted due to the need to dispose of them in optical or sewer systems toilets. If wet strength is imparted to these products, a fleeting wet strength, characterized by a decay or part of the initial strength at the time of laying in the presence of water, is preferred. If a fugitive wet strength is desired, the binder materials may be selected from the group consisting of dialdehyde starch or other resins with aldehyde functional groups such as Co-Bond 1000® offered by National Starch and Chemical Company of Scarborough, ME; -Parez 750® offered by Cytec of Stamford, CT; and the resin described in U.S. Patent 4,981,557, issued January 1, 1991 to Bjorkquist, the disclosure thereof is incorporated herein by reference and other resins that have the decay properties described above as they can. known in the art. If improved absorbency is needed, the surfactants can be used to treat the tissue paper webs of the present invention. The level of surfactant, if used, is preferably between about 0.01% and 2.0% by weight, based on the dry fiber weight of the tissue web.

The surfactants preferably have alkyl chains with eight or more carbon atoms. Anionic surfactants, eg, enzymes, include linear sulfonates and alkylbenzene sulphonates. Exemplary nonionic surfactants include alkyl glycosides including alkylglycoside esters such as Crodesta SL-40® which is available from Croda, Inc. (New York, NT); alkyl glycoside ethers as described in U.S. Patent 4,011,389, issued to Langdon, et al. March 8, 1977; and alkyl polyethoxylated esters such as - Pegosperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520® available from Rhone Poulenc Corporation (Cranbury, NJ). Alternatively, the softening, cationic active ingredients with a high degree of unsaturated mono and / or poly and / or branched chain alkyl groups can be greatly improved in their absorbency characteristic. The cellulosic structures of the present invention may also contain other types of chemical softeners. For example, another class of chemical softening agents added to papermaking comprise the well-known organo-reactive polydimethyl siloxane ingredients, among which the most preferred amino functional polydimethyl siloxane is included. Loading materials may also be incorporated into the tissue papers of the present invention. U.S. Patent 5,611,890, issued to Vinson et al. on March 18, 1997 and which is incorporated herein by reference exhibits loaded tissue paper products that are acceptable as substrates for the present invention. The above lists of optional chemical additives are simply intended to be exemplary in nature and are not intended to limit the scope of the invention.

Addition Method Preparation of the Paste Referring to Figure 2, additional insight can be obtained in the preparation of the methods for the aqueous pulp, which is a schematic representation illustrating a preparation of the aqueous pulp for the operation of the creped papermaking that provides a product according to the present invention. The following analysis refers to Fi gu 2: A storage container 8 is a reservoir for the low viscosity chemical softening composition of the present invention. A tube 9 provides dilution water to reduce the concentration of the softening active ingredient to a concentration of suitable use. The pump 10 acts to transport the dilute vesicular dispersion of the softening active ingredient. The dispersion is optionally conditioned in. a mixer 12 to aid in the formation of the vesicles. The resulting dispersion 13 is transported to a point where it is mixed with an aqueous dispersion of relatively long, refined fiber paper fibers. Referring still to Figure 2, a storage container 1 is provided to continue to fence an aqueous pulp of relatively long paper fibers. The pulp is transported by means of a pump 2 and optionally through a refiner 3 to fully develop the strength potential of the long papermaking fibers. Can use the tube 27 positioned between the pump 2 and refiner 3 to add a cationic disintegrating agent, if desired, to offset the fine charged to minimize the use of , ^^ ^^ í í ^ S ^^^ ^ s ^ ~ &! M ^^ & rj other materials added to later stages in the process. If desired, the addition tube 4 carries a resin to provide a wet or dry strength in the finished product. The pulp is then further conditioned in a mixer 5 to aid in the absorption of the resin. After mixing with the vesicular dispersion of the softening active ingredient 13, it becomes the relatively long fiber based on the aqueous pulp 17. Optionally, the pulp can be conditioned in a mixer 25 to aid in the absorption of the softening active ingredient. The suitably conditioned pulp is then diluted with foaming water 7 in a fan pump 6 to form a pulp 29 of long paper fiber. The tube 20 adds a cationic flocculant to the pulp 29, producing a pulp 22 of relatively long, flocculated fiber. Still referring to Figure 2, a relatively short fiber pulp pulp originates from a reservoir 11, which is transported through the tube 49 via the pump 14 through a refiner 15, where it becomes a refined pulp of relatively short paper fibers 16. Foamy water 7 is mixed with pulp 16 in a pump with fan 18 at which point, the pulp becomes an aqueous, diluted paper pulp 19. The tube 21 directs a cationic flocculant in the pulp 19, after which the pulp becomes a relatively short, aqueous, flocculated fiber, based on the pulp 23. In a mode of a papermaking process, the pulp 23, Aqueous, based on relatively short flocculated fibers, is directed to the creping paper process illustrated in Figure 1 and divided into two approximately equal streams which are then directed towards the head chambers 82 and 83 which evolve last in the layer 75 on the outside of the Yankee side and the layer 71 on the Yankee side, respectively of the soft and resistant creped tissue paper. Similarly, the pulp 22 of the relatively long, flocculated, aqueous paper fiber, referred to in Fig. 2, is preferably directed towards the head chamber 82b evolving ultimately into the central layer 73 of the paper crepe tissue soft and resistant.

The creping process Papelero Figure 1 is a schematic representation illustrating a creped papermaking process for producing a soft and strong creped tissue. These preferred embodiments are described in the following analysis, where reference is made to Figure 1. Figure 1 is a side elevational view of a paper machine 80 preferred for papermaking according to the present invention. 10 invention. Referring to Figure 1, the paper machine 80 comprises a layered head 81 having an upper chamber 82, a central chamber 82b, and a lower chamber 83, a plate ceiling 84 and a Fourdrinier mesh 85 with which it is made a 15 lacing on the breastplate roller 86 and around it, the deviator 90, the vacuum suction boxes 91, the bed roller 92 and a plurality of rotating rollers 94. In operation, a pulp is pumped through the upper chamber 82 20 and a second pulp is pumped through the central chamber 82b, while a third pulp is pumped through the lower chamber 83 and thus out of the plate roof 84 onto the Fourdrinier mesh 85 to form therein a plot 25 embryo 88 comprising layers 88a, 88b and 88c.

The draining occurs through the Fourdrinier mesh 85 and is assisted by a diverter 90 and vacuum boxes 91. As the Fourdrinier mesh is made, it returns in a run in the direction shown by the arrow, sprinklers 95 they clean before starting another pass on the breast roller 86. In the wet transfer zone 93, the embryonic web 88 is transferred to a foraminous carrier fabric 96 by the action of a vacuum transfer case 97. The carrier fabric 96 transports the weft from the transfer zone 93 after the vacuum draining box 98, through presechers 100 per puff and after the two rotating rollers 101, after which the weft is transferred to a dryer Yankee 108 by the action of a pressure roller 102. Carrier fabric 96 is then cleaned and drained as it is completed by passing it over and over additional and further roller rollers 101, sprinklers 103 and the draining box 105 vacuum. The paper web is secured with adhesive to the cylindrical surface of the Yankee dryer 108 aided by adhesive applied by a spray applicator 109. Drying is carried out on the Yankee dryer 108 heated with steam and rjfea &naii hot air, which is heated and circulated through the drying hood 110 by means not shown. The weft is then dry creped from the Yankee dryer 108 by a scraper blade 111 after which the paper sheet 70 is formed comprising a Yankee side layer 71, a core layer 73, and a layer 75 off the Yankee side. The sheet of paper 70 is then passed between the calender rolls 112 and 113, around a circumferential portion of the reel 115 and by rolling it on a roller 116 on a core 117 placed on the shaft 118. Still referring to Figure 1 , the origin of the Yankee side layer 71 of the paper sheet 70 is the paste pumped through the lower chamber 83 of the head 81 and the same paste is applied directly to the Fourdrinier mesh 85 after which the layer becomes 88c of the embryonic web 88. The origin of the central layer 73 of the paper sheet 70 is the paste supplied through the chamber 82.5 of the head 81 and the same paste forms the layer 88b on top of the layer 88c. The origin of the side layer outside the Yankee 75 of the paper sheet 70 is the paste supplied through the upper chamber 82 of the head 81 and which forms the layer 88a on the upper part of the layer 88b of the embryonic web 88. Although Figure 1 shows a paper machine 80, having a head 81 adapted to manufacture a three-layer weft, the head 81 can alternatively be adapted to produce single-layer, two-layer or other multi-layer wefts. Further, with respect to the manufacture of the paper sheet 70, which incorporates the present invention in the paper machine 80, Figure 1, the Fourdrinier mesh 85 must be of a fine weft having relatively small openings with respect to the average lengths of the fibers that make up the short fiber pulp in such a way that a good formation is present; and the foraminous carrier fabric 96 should have a fine weave having relatively small openings with respect to the average lengths of the fibers constituting the long fiber stock to substantially obviate the bulkiness of the fabric side of the embryonic web in the spaces int er filamentous of the fabric 96. Also, with respect to the process conditions for the exemplary manufacture of the paper sheet 70, the paper web is preferably dried to approximately 80% fiber consistency and more preferably approximately 95% fiber consistency. % fiber consistency before creping. In general, the present invention can be applied to creped tissue paper, which includes, incidentally, creped tissue paper conventionally pressed with felt; creped and densified tissue paper with high bulk pattern; and crepe tissue without compaction, high voluminosity. Someone with experience in the technique also 10 will recognize that the steps of the process described above are exemplary and that other processes are equally within the scope of the present invention. For example, a homogeneous paste can be provided, wherein the paste can 15 comprising any desired mixture of long and short paper fibers that have been treated with a vesicular dispersion of a chemical softening active ingredient using the process steps similar to those described above. The Processes that provide tissue structures having two layers, such as those shown in Examples 3 and 4, are also within the scope of the present invention.

EXAMPLES Example 1 This example illustrates the preparation of a preferred embodiment of the softening composition of the present invention. The materials used in the preparation of the chemical softening mixture are: 1. Quaternary ammonium compound of tallow diester partially hydrogenated chloride, pre-mixed with polyethylene glycol 400 and a non-ionic surfactant with ethoxylated fatty alcohol. The premix is a quaternary ammonium compound of approximately 69% (Adox SDMC-type from Witco incorporated) 29% PEG 400 (available from JT Baker Company of Phil lipsburg, NJ) and 2% non-ionic (available from Shell Chemical of Huston, TX as Neodol 91-8). The mixture is available from Witco as DXP-5429-14. 2. Calcium Chloride Granules: from J. T. Baker Company of Phi 11 ipsburg, NJ. 3. Polydimethylsiloxane: 10% active emulsion (DC2310) from Dow Corning of Midland, MI. 4. Hydrochloric acid (25% solution) from J. T. Baker Company of Phi 1 lipsburg, NJ.

Ste & ms ^ s ?? Jk & and 5. HOE stabilizer S 4060, from Clariant Corp., Charlotte, NC. These materials are prepared as follows to form the softening composition of the present invention. The chemical softening composition is prepared by first heating the required amount of water to approximately 75 ° C. The hydrochloric acid and the polydimethexysiloxane are then added to the hot water. The pH of the water premix is about 4. The premix of the quaternary compound, PEG 400 and the nonionic surfactant are then heated to about 65 ° C and dosed into the aqueous premix with stirring until the mixture becomes completely homogeneous . Approximately half of the calcium chloride is added as a 2.5% solution in water with continuous agitation. The stabilizer is then added with continuous stirring. The reduction of the final viscosity is achieved by adding the remaining calcium chloride (as a 25% solution) with continuous mixing. The components are mixed in a sufficient proportion to provide a composition having the following approximate concentrations of each of the ingredients. ? -s? l? w **. 40. 1% Quaternary ammonium compound of tallow diester partially hydrogenated chloride c.b.p. Water 17.2% PEG 400 1.1% Neodol 91-8 0.6% CaCl2 0.5% Stabilizer 0.02% Polydimethylsiloxane 0.02% HCl After cooling and addition of the constituent water, the composition has a viscosity of about 300 centipoise as measured at 25 ° C and at a shear rate of 100 sec "1 using the method described in the TEST METHODS section.

Example 2 This example illustrates the effect of the non-ionic surfactant gum composition on a viscosity property of the key softening composition. The guanic softening compositions are first constituted by preparing a masterbatch containing all the ingredients of the softening composition except for a bilayer breaking agent. a ^? t &itffca-; - ^. ^^ .- a The formula for this composition is given in Table 1.

Table 1 Component Concentration (%) Quaternary ammonium compound of tallow diester chloride partially 41 hydrogenated Water 3.9 PEG 400 19 CaCl2 0.6 Stabilizer 0.5 Polydimethylsiloxane 0.02 HCl 0.02 The test softening compositions are then prepared by mixing potential bilayer cleaving agents with the master batch at 1% levels, 2%, 3% and 4%. The viscosity of each of these test softening compositions is measured according to the method described in the following section of TEST METHODS. The viscosity of the master batch is also measured. Table 2 shows the test materials, their HLB (a measure of the emulsifying efficiency) and the viscosity of each of the compositions made. TABLE 2 Non-ionic surfactant HLB Concentrate Viscosity (%) [centipoise] Neodol 23-31 7.9 0 1.8xl07 * 1 6774 2 4375 3 1549 4 1365 NEODOL 23-51 10.7 0 2150 * 1 335 2 260 3 644 4 1285 NEODOL 91-í 13.9 0 1.8x107 * 1 166 2 1583 3 9xl05 4 8xl06 Surfonic N-120 '14.1 0 6103 * 1 193 2 704 3 7595 9X10b Acconon CC-i 6103 * 450 421 1194 1.7x10' Tween 60 14.9 6.4xl07 * 215 367 652 2043 Plurafac B25-5"12.0 1029 * 442 2100 2.9x10" 1. lxlO7 * Without being limited by theory, it is believed that the capacity of variation in viscosity is due to the intermittent formation of stable liquid crystalline phases due to the high concentration of the softening active ingredient used. As noted above, the addition of the bilayer breaking agent is believed to reduce this viscosity by disrupting the structure of the liquid crystalline phase. 1. Ethoxylated fatty alcohol from Shell Chemical, Houston, TX 2. Ethoxylated alkylphenol from Huntsman Corp., Houston, TX 3. Capric / ethoxylated capric glyceride from Abitec Corp. of Columbus, OH 4. POE (20) Sorbitan monostearate from Henkel Corp. Charlotte, NC 5. Oxyethylated straight chain alcohol modified from BASF Corp., Mt. Olive, NJ As can be seen, each of these materials practically reduces the viscosity of the dispersion to a viscosity lower than that of the dispersion without the material.

EXAMPLE 3 The purpose of this example is to illustrate a method using a conventional drying papermaking technique for making absorbent and soft tissue treated with a chemical softening composition of the prior art comprising a premix of Disebo Methyl Sulphate (Hydrogenated) DiMetil Ammonium (DHTDMAMS) and a Polioxiet ílengl icol 400 (PEG-400) in solid state and an additive resin of wet strength. A pilot scale S-wrap twin mesh paper machine is used in the practice of the present invention. First, a chemical softening composition is prepared to virtually water-free self-emulsifiable according to U.S. Patent 5,474,689 wherein the homogeneous premix of DHTDMAMS and PEG-400 in the solid state are dispersed in a water tank conditioned (Temperature of approximately 66 ° C) to form a sub-micronic vesicular dispersion. Second, a 3% by weight aqueous pulp of Deinked Market Pulp (DMP) is produced in a conventional pulper. The DMP pulp is gently refined and a 0.25% solution of the wet strength resin (ie, Kymene 557H as available from Hercules of Wilmington, DE) is added to the tube of the DMP material at a rate of 0.7 pounds resin / ton (.04%) by weight of the dry fibers. The adsorption of the wet strength resin in the DMP fibers is improved by an in-line mixer. The DHTDMAMS in the form of a chemical softening mixture according to U.S. Patent 5,474,689 is also added to the tube of DMP material (at a concentration of 1% softener active ingredient) before being added to the material pump, but after the wet strength resin, at a rate of approximately 2.5 pounds / ton (0.125%) by weight of the fibers in dry. The adsorption of the chemical softening mixture to the DMP fibers can be improved with an in-line mixer. The DMP pulp is diluted to approximately 0.2% consistency in the fan pump. Third, a 3% by weight aqueous pulp of Eucalyptus fibers is made in a conventional re-pulper. The eucalyptus pulp is diluted to approximately 0.2% consistency in the pump with fan. The DMP and eucalyptus pulps are directed to a multi-channel head equipped suitably with sheets in layers to keep the streams as separate layers until they are discharged into a double mesh S-wrap in motion. A three-chamber head is used. The eucalyptus pulp, which contains enough solids, flows to achieve 34% dry weight of the last paper is directed towards the conduction chambers for the forming mesh, while the DMP pulp comprising sufficient solids flows to achieve 66% dry weight of the last paper which is directed towards the remaining two chambers. The pulps of DMP and eucalyptus are combined in the -discharge of the head in the compound pulp. The composite pulp is discharged onto the double mesh S-wrap in anterior movement and drained. The drainage is helped by a diverter and vacuum boxes. The embryonic wet web is transferred from the previous S-wrap double mesh, to a fiber consistency of approximately 15% at the point of transfer to a drying fabric. A suitable drying fabric is a needle-punched cotton sheet with a three-ply base fabric as available from Al-bany International of Albany, NY as TRIOVENT. An additional draining is carried out by drain-assisted vacuum until the web has a fiber consistency of approximately 28%. The semi-dry web is then adhered to the surface of a Yankee dryer with a sprayed creping adhesive comprising a mixture of polyvinyl alcohol and a polyamide-based resin. The creping adhesive is supplied to the Yankee surface at a rate of 0.125% adhesive solids based on the dry weight of the weft. The fiber consistency is increased to approximately 96% before the weft is creped dry from the Yankee with a scraper blade. The scraper blade has a chamfered angle of approximately 20 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of approximately 76 degrees. The crepe percentage is adjusted to approximately 21-25% when operating the Yankee dryer at a rate of approximately 1000 fpm (feet per minute) (approximately 305 meters per minute), while the dry pattern is formed on a roller at a speed of approximately 770 fpm (235 meters per minute). The tissue paper has a basis weight of approximately 10 pounds / 3000 ft2 (16 grams / m2), contains approximately 0.1% of the self-emulsifiable chemical softener mixture practically without water and approximately 0.1% of the wet strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as a facial tissue and / or toilet paper.

^^^^^^^^^^^ EXAMPLE 4 The purpose of this example is to illustrate a method using a conventional drying papermaking technique to make soft and absorbent tissue paper treated with a chemical softener composition of low viscosity prepared according to Example 1 of the present invention and a wet strength resin. The production of the paste is practically the same as that used in Example 1, the only exception being that a 2.5% dispersion of the chemical softening mixture of Example 1 is used in place of the chemical softening composition of the prior art. The separated pastes are supplied to a head, are deposited in an anterior double mesh and are dried in practically the same manner as described in Example 1 to form a dry tissue web. The tissue paper has a basis weight of approximately 10 pounds / 3000 ft2 (16 grams / m2), contains approximately 0.05% of the self-emulsifiable chemical softener mixture with virtually no water and approximately 0.1% of the dry strength resin. Importantly, the paper The resulting tissue is soft, absorbent and is suitable for use as a facial tissue and / or toilet paper.

Example 5 This example compares the properties of the tissue papers of Examples 3 and 4.

Sample of Base Weight Resistance to Resistance to Retention of] Tissue (grams / m ') Tension in MD Te: nsion in CD Softener (g / cm) (g / cm) (%) Example 3 16 62.6 42.5 17.2 Example 4 16.5 • 75.2 44.8 16.8 As can be seen, the tissue papers produced in Examples 3 and 4 have practically the same physical properties.

TEST METHODS Softening Active Ingredient Level on cellulose fibers The analysis of the amounts of softening active ingredients described herein gue retained on cellulosic structures may be performed by any method accepted in the applicable art. These 1 ± KJ) 1? - - zSjzt.r The methods are empli ficative and do not intend to exclude other methods that may be useful in determining the levels of the particular components retained by the tissue paper. The following method is suitable for determining the amount of preferred quaternary ammonium compounds (QAC) that can be deposited by the method of the present invention. A solution of standard anionic surfactant (sodium dodecyl sulfate-NaDDS) is used to titrate the QAC using an indicator of dimide bromide.

Preparation of Standard Solutions The following methods are applicable for the preparation of the standard solutions used in this titration method.

Preparation of the Dimidio Bromide Indicator To a 1-liter volumetric flask: A) Add 500 milliliters of distilled water. B) Add 40 ml of dimide bromide disulphide blue indicator material solution available from Gallard-Schlesinger Industries, Inc. of Carie Place, NY. $ & tr y.

C) Add 46? ßl of H2S04 5N D) Fill the flask to the mark with distilled water and mix. Preparation of the NaDDS solution: To a 1 liter volumetric flask: A) Weigh 0.1154 grams of NaDDS available from Aldrich Chemical Co. of Milwaukee, Wl as sodium dodecyl sulfate (ultra pure). B) Fill the flask to the mark with distilled water and mix to form a 0.0004N solution.

Method On an analytical balance, weigh approximately 0.5 grams of a sample of the cellulosic fiber structure. Record the weight of the sample to the nearest 0.1 mg. Place the sample in a glass cylinder that has a volume of approximately 150 milliliters containing a stirrer magnetic stirrer. Using a graduated cylinder, add 20 milliliters of methylene chloride. In a steam hood, place the cylinder on a hot plate turned to reduce heat. Have the solvents boil completely while stirring and using a fr-lttfflf ^^ graduated cylinder, "" add 35 milliliters of indicator solution of dimide bromide. While it is shaking to & amp;; * &fca speed, bring the methylene chloride to a full boiling point again. Stop heating, but continue stirring the mixture. The QAC will be complexed with the indicator that forms a blue compound in the methylene chloride layer. Use a 10 ml burette, titrate the sample with an anionic surfactant solution. This is done by adding an aliquot of titrant and stirring rapidly for 30 seconds. Stop the stirring plate, allow the layers to separate and check the intensity of the blue color. If the color is dark blue add approximately 0.3 milliliters of titrant, shake rapidly for 30 seconds and turn off the agitator. Check again the intensity of the blue color. Repeat if necessary with another 0.3 milliliters. When the blue color begins to turn pale, add the titrant drop by drop between the agitations. The end point is the first sign of a pale pink color in the methylene chloride layer. - * e S ^ 3tá ^ -z ^ H ~ z.7 ^ yi 6. Record the volume of titrant used to the nearest 0.05 ml. 7. Calculate the quantity of QAC in the product using the equation: (milliliters of NaDDS - X)? Y 2 = Pounds Per Ton QAC Sample Weight (Grams) Where X is a correction space obtained from the holder of a sample without the QAC of the present invention. And it's the milligrams of QAC that 1.00 milliliters of NaDDS will title. (For example, Y = 0.254 for a particularly preferred QAC, i.e., di-di-ester di (hydrogenated to the touch) tallow dimethyl ammonium.) DENSITY The density of a cellulosic structure (eg, paper), in the sense in which it is used in the present, the term "density", is the average density calculated as the basis weight of that paper divided by the caliber, with the appropriate unit conversions incorporated into the present. The caliber of the paper, in the sense in which it is used in the present, is the thickness of the paper when - »« V * I * is subjected to a pressure of 95 g / inch (15.5 g / cm2). RESISTANCE OF PAPERS TISU 5 Resistance to Dry Stress This method is intended to be used on finished paper products, spool samples and uncoated materials. The tensile strength of these products can be determined on 10-inch-wide strips of the sample - using a Thwing-Albert Intelect II Standard Stress Tester (Thwing-Albert Instrument Co of Philadelphia, PA).

Conditioning and Sample Preparation 15 Prior to the stress test, the paper samples to be tested should be conditioned for at least 15 minutes at a relative humidity of 48 to 52% and in a temperature range of 22 to 24 ° C. . The preparation of the sample and all 20 aspects of the stress test should also be carried out within the confines of the constant temperature and ambient humidity. For the finished product, discard any damaged product. Then, remove 5 strips 25 of four usable units (also called ^ fifife? ... ": to sheets) and stack one on top of the other to form a large stack with the perforations between the matching sheets Identify sheets 1 and 3 for voltage measurements in the machine direction and sheets 2 and 4 for tension measurements in the transverse direction, then cut through the perforation line using a paper cutter (JDC-1-10 or JDC-1-12 with Thwing-Albert safety protection) Instrument Co. of Philadelphia, PA) to make 4 batteries separately.Make sure that batteries 1 and 3 are still identified for the test in the machine direction and batteries 2 and 4 are identified for the test in the transverse direction. 2 1"strips in the machine direction of stacks 1 and 3. Cut two 1" strips in the transverse direction of stacks 2 and 4. There are now four 1"wide strips for the tension test in the machine direction and four 1"wide strips for the pru Tension in the transverse direction. For these finished product samples, the eight 1"wide strips are five usable units (also called sheets) of thickness.

For the unconverted pile and / or the spool samples, cut a 15"by 15" sample which is 8 folds thick from a region of interest of the sample using a paper cutter (JDC-1-10 or JDC-1-12 with a safety cover by Thwing-Albert Instrument Co of Philadelphia, PA). Make sure that a 15"cut runs parallel to the machine direction while another runs parallel to the transverse direction.Make sure the sample is conditioned for at least 2 hours at a relative humidity of 48 to 52% and within a temperature range from 22 to 24 ° C. The preparation of the sample in all aspects of the stress test should also be carried out within the confines of the constant temperature and the humidity of the environment. 15"by 15" preconditioned which has 8 thick folds, cut four strips of 1"by 1" with the dimension of 1"long running parallel in the machine direction. Observe these samples as the spool in the machine direction or as samples of unconverted material. Cut about four additional 1"by 7" strips with the dimension of 1"long that runs parallel in the transverse direction.

M t ^^^ j ** »* Observe these samples as a spool in the transverse direction or samples of unconverted material. Make sure all previous cuts are made using a paper cutter (JDC-1-10 or JDC-1-12 with a safety jacket from Thwing-Albert Instrument Co. of Philadelphia, PA). There are now a total of eight samples: four strips of 1 '-' by 1"which have 8 sheets of thickness with the dimension of 1" that run parallel to the machine direction and four strips of 1"by 7" that They have 8 sheets of thickness with the dimension of 1"running parallel to the transverse direction.

Stress Tester Operation For the actual measurement of the tensile strength, use a Thwing-Albert Intelect II Standard Stress Tester (Thwing-Albert Instrument Co. of Philadelphia, PA). Insert the flat-faced clamps into the unit and calibrate the tester in accordance with the instructions provided in the Thwing-Albert Intelect II operation manual. Adjust the crosshead speed of the instrument to 4.00 inch / minute and the Ia and 2nd gauge lengths to 2.00 inches. The breaking sensitivity should be adjusted to 20.0 grams and the sample width should be adjusted to 1.00"and the thickness of the sample to 0.025". A load cell is selected in such a way that the result of the voltage predicted for the sample to be tested rests between 25% and 75% of the interval in use. For example, a 5000 gram load cell can be used for samples with a predicted voltage range of 1250 grams (25% of 5000 grams) and 3750 grams (75% of 5000 grams). The tension adjuster can also be adjusted in the range of 10% with the 5000 grams of load cell so that samples can be tested with the predicted voltages of 125 grams to 375 grams. • Take one of the tension strips and place one end of it in a clamp of the tension tester. Place the other end of the paper strip in the other clamp. Make sure that the length of the strip is running parallel with the sides of the voltage tester. Also make sure that the strips do not hang on both sides of the two clamps. In addition, the pressure of each of the clamps must be in total contact with the paper sample.

After inserting the paper test strip into the two clamps, the instrument voltage should be monitored. If a value of 5 grams or more is shown, the sample is too stiff. Conversely, if a period of 2 to 3 seconds elapses after starting the test before any value is recorded, the tension strip is too loose. Turn on the voltage tester as described in the manual of the voltage tester instrument. The test is completed after the crosshead automatically returns to its initial starting position. Read and record the voltage load in units of grams of the scale of the instrument or the digital panel meter to the nearest unit. If the reset condition is not automatically performed by the instrument, make the necessary adjustment to adjust the clamp of the instrument to its initial starting positions. Insert the next paper strip into the two clamps as described above and obtain a tension reading in units of grams. Obtain tension readings from all paper test strips. It should be noted that the readings should be discarded if the strip slips or breaks at the edge of the clamps while the test is performed.

Calculations For the four strips of the finished product of a width of 1"in the machine direction, add the four individually recorded tension readings, divide this sum by the number of strips tested, this number should normally be four, and also divide the sum of the tensions recorded between the number of usable units per tension strip.This is normally five for both 1-sheet and 2-sheet products.Repeat this calculation for the strips of the finished product in the transverse direction. or uncovered reel, cut in the machine direction, add the four individual recorded voltage readings. Divide this sum by the number of strips tested. This number should normally be four. Also divide the sum of the voltages recorded between the number of usable units per voltage strip. This is normally eight.

Repeat this calculation for the strips of un-converted sample paper or reel in the transverse direction. All results are presented in units of grams / inch. For the purposes of this specification, the tensile strength must be converted to "total specific stress resistance" defined as the sum of the tensile strength measured in the machine and transverse directions to the machine, divided by the weight base and corrected in units for a value in meters.

VISCOSITY General Viscosity is measured at a shear rate of 100 (s "1) using a rotating viscometer, the samples are subjected to a linear voltage sweep, which applies a range of voltages, each at a constant amplitude.

Apparatus Viscometer Rheometer of T $ gM Dynamics Model SR500 which is available from Rheometrics Scientific, Inc. of Piscatawy, NJ Sample Plates 25 mm parallel insulated plates are used Ate Aperture 0.5 mm Sample Temperature 20 ° C Sample Volume At least 0.2455 cm3 Initial Cutting Stress Tension 10 dynes / cm2 Final Cutting Stress Tension 1,000 dynes / cm "'2- Tension increase 25 dynes / cm applied every 20 seconds Method Place the sample on a sample plate with an opening. Close the opening and operate the rheometer in accordance with the manufacturer's instructions to measure the viscosity as a function of shear stress between the initial shear stress and the final shear stress using the voltage increase defined in the above .

Result and Calculation The logarithmic shear velocity plotted on the resulting graphs (s "1) on the x axis, the logarithmic Poise viscosity (P) on the left axis and the stress (dynes / cm2) on the y axis of the The viscosity values are read at a shear rate of 100 (s_1) .The values for viscosity are converted from P to centipoises (cP) by multiplying by 100. The exposures of all patents, patent applications ( and any patents that are granted therefrom, as well as any corresponding published patent applications), and the publications mentioned throughout this description are incorporated herein by reference, however, it is not expressly admitted that any the documents incorporated by reference herein show or set forth the present invention, while the particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended to cover all these changes and modifications within the scope of this invention in the appended claims. ^ < ^ fe, ^^^ £ ,, ^ A1,3 ^ a ^

Claims (10)

1. CLAIMS 1. A method for providing a soft tissue product, the method comprising the steps of: a) providing a chemical softening composition characterized in that the chemical softening composition comprises: a vehicle; a softening active ingredient, wherein the softening active ingredient comprises a quaternary ammonium compound; an electrolyte; and a bilayer breaking agent; b) diluting the chemical softening composition to a use concentration; c) providing pulp of paper fibers; d) treating the pulp of paper fibers with the diluted chemical softening composition; e) depositing the treated pulp of the paper fibers on a foraminous forming mesh; and f) draining the treated pulp by draining the foraminous forming mesh to form an embryonic web. 3. The method according to claim 1, wherein: a) the pulp of paper fibers comprises separate pulps, a first pulp of relatively short paper fibers and a second pulp of relatively long paper fibers; b) only the second pulp is treated with the diluted chemical softening composition; and c) the first pulp is placed in a foraminate fabric between the mesh and the second pulp. 3. The method according to Claims 1 or 2, wherein the softening active ingredient comprises at least about 25% of the composition, preferably at least about 35% of the composition. 4. The method according to any of the preceding claims, wherein the softening active ingredient comprises a quaternary ammonium compound, preferably the softening composition comprises a quaternary ammonium compound having the formula: (R 1 I 4-ra 'N + - [(CH2) nY-R3] mX' where Y is -0- (0) C-, or -C (0) -0-, or -NH-C (O ) -, or -C (0) -NH-; m is 1 to 3, preferably 2, n is 0 to 4, preferably 2, each Ri is an alkyl or alkenyl group of Ci-Cd, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof, each R3 is a C3-C2 alkyl or alkenyl group, a hydroxyalkyl group, a hydrocarbyl group or a substituted hydrocarbyl group, alkoxylated group, a benzyl group or mixtures thereof, preferably R3 is Ci5-C7 alkyl or alkenyl, and X "is any anion compatible with the softener, preferably X" is chloride or methyl sulfate. 5. The method according to any of the preceding claims, wherein the composition further comprises a plasticizer, preferably the plasticizer is selected from the group consisting of polyethylene glycol, polypropylene glycol and mixtures of the same. taüstl.abks ^ =. 6. The method according to any one of the preceding claims, wherein the carrier is water and the electrolyte is a salt selected from the group consisting of sodium, calcium and magnesium chloride salts. 7. The method according to Claim 6, wherein the salt is present at a level between about 0.1% and 20% by weight of the composition. 8. The method according to any of the preceding claims, wherein the bi-layer breaking agent is used at a level between about 2% and 15% of the level of the softening active ingredient. 9. The method according to any of the preceding claims, wherein the bilayer cleaving agent is selected from the group consisting of: i. nonionic surfactants derived from amine, amide, fatty amine-oxide alcohol, fatty acid, alkyl phenol and / or saturated and / or unsaturated primary, secondary and / or branched alkyl aryl carboxylic acid compounds, having from T - '? £ zz about 6 and 22 carbon atoms in a hydrophobic chain, wherein at least one active hydrogen of the compounds is ethoxylated with < 50 ethylene oxide entities to provide an HLB of between about 6 and 20, preferably, the bi-layer breaking agent is a nonionic surfactant having a hydrophobic entity that is selected from the group consisting of: fatty alcohols having between about 8 and 18 carbon atoms and alkyl phenols having between about 8 and 18 carbon atoms, wherein the hydrophobic entity is ethoxylated with between about 3 and 15 ethylene oxide entities; ii. nonionic surfactants with bulky main groups selected from: a. surfactants that have the formulas: where Y "= N or O; and each Rl is selected independently of the following: -H, -OH, - (CH2) XCH3, -0 (OR2) zH, -OR1, -OCfOJR1, and -CH (CH2- (OR2) Z-H) -CH2- (OR2) Z-C ( O) R1, x and R1 are as defined above and 5 < z, z 'and z "< 20; and b) polyhydroxy fatty acid amide surfactants of the formula: R2-C (O) - (R1) -Z wherein: each R 1 is H, C 1 -C 4 hydrocarbyl C 1 -C 4 alkoxyalkyl or hydroxyalkyl; R2 is a hydrocarbyl entity of C5-C2 ?; and each Z is a polyhydroxyhiarocarbyl entity having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain or an ethoxylated derivative thereof; and iii. cationic surfactants having the formula: (R Y- [(R -0) Z-H] P.}. + X " wherein R1 is selected from the group consisting of alkyl or saturated or unsaturated, primary, secondary or branched alkyl aryl hydrocarbons; the hydrocarbon chain has between about 6 and 22 carbon atoms; each R2 is selected from the following groups or combinations * -it? t- of the following groups: - (CH2) n- and / or - [CH (CH3) CH2] -; And it is selected from the following groups: = N + - (A) q; - (CH2) n-N + - (A) q; -B- (CH2) n-N + - (A) 2; - (feni lo) -N + - (A) q; - (B-feni lo) -N + - (A) q; with n that is between approximately 1 and 4, where each A is independently selected from the following groups: H; alkyl of C? _5; R1; - (R20) z-H; - (CH2) ZCH3; phenyl and substituted aryl; where 0 < x < approximately 3; and each B is selected from the following groups: -O-; -NA -; - NA2; -C (0) 0-; and -C (0) N (A) -; wherein R2 is defined as above; q = l or 2; Total z per molecule is between about 3 and 50; and X "is an anion that is compatible with fabric softening active agents and adjunct ingredients. 10. The method according to any of the preceding claims, wherein the use concentration is between about 0.5% and 10%, preferably the use concentration is between about 0.5% and 5%, most preferably the usage concentration is about 1. %. JS & a Sy? ^^ ySS j