CN106906573B

CN106906573B - The fibre structure containing active material of multiple regions with different densities

Info

Publication number: CN106906573B
Application number: CN201710007191.8A
Authority: CN
Inventors: P·T·威斯曼; A·J·德瑞赫; M·R·斯维克; A·H·哈马德-易卜拉欣伯; G·C·戈登; P·D·乔克翰
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd
Priority date: 2012-01-04
Filing date: 2013-01-03
Publication date: 2019-08-27
Anticipated expiration: 2033-01-03
Also published as: RU2014126639A; JP5964453B2; MX2014008195A; FR2985272B1; BR112014016643A2; EP3369845A1; ZA201404643B; WO2013103626A1; GB2498443B; EP2800802A1; GB201300045D0; CN106906573A; US20130171421A1; EP2800802B1; FR2985272A1; CA2860647A1; BR112014016643A8; CA2860647C; EP3369845B1; CN104039945A

Abstract

There is provided herein a kind of fibre structures, it includes long filament, wherein the long filament includes one or more long filament forming materials and the one or more activating agents that can be discharged from the long filament when being exposed to expected use condition, wherein the fibre structure also has at least two regions with different averag densities.The method with fibre structure processing fabric is also provided herein.

Description

Fibrous structure containing active substance having multiple regions of different densities

The present application is a divisional application of chinese patent application No.201380004748.2 entitled "active material-containing fibrous structure having a plurality of regions of different densities" filed on 3/1/2013.

Technical Field

The present disclosure relates generally to fibrous structures comprising one or more active agents and further comprising distinct regions, and in particular, the fibrous structures having regions of different densities, and methods of making the same.

Background

Fiber structures are known in the art. For example, polyester nonwoven fabrics impregnated and/or coated with detergent compositions are known in the art, as shown in prior art fig. 1 and 2. As shown in fig. 1 and 2, a known nonwoven substrate 10 is made from insoluble fibers 12, wherein the nonwoven substrate 10 is coated and/or impregnated with an additive 14, such as an active agent. An example of such a web of material may beFull 3 in 1 laundry tablets are commercially available from The Dial Corporation.

In addition, non-fibrous articles formed from the casting solutions of detergent compositions are also known in the art and are useful as detergent compositionsLaundry tablets are commercially available, which are commercially available from Dizolve Group Corporation.

However, such known material webs and/or articles exhibit negative effects, which can be problematic for consumers. For example, known webs of material and/or articles are relatively rigid and/or inflexible and therefore prone to breaking upon simple handling. Furthermore, the web of material and/or the article typically delivers such low levels of detergent composition and/or detergent active that the cleaning performance is below the consumer's expectations. Another negative effect is that the web of material and/or the article may leave a residual portion of the web of material and/or the article after the washing operation, e.g., the polyester nonwoven substrate does not dissolve during the washing operation. Another negative effect of such known material webs is that they have a potential tendency to stick to the washing machine surface or window during the wash cycle and thus not function in delivering their intended use, i.e. cleaning the clothing. Most importantly, known webs of material can, in some instances, clog the drainage mechanism of washing machines. Additional negative effects include removing the insoluble carrier substrate of the article, such as discarding the polyester nonwoven substrate.

Accordingly, the present invention provides a fibrous structure comprising one or more active agents and filaments such that the fibrous structure comprises two or more regions having different strength characteristics for improved strength while providing sufficient dissolution and disintegration during use.

Disclosure of Invention

According to one embodiment, a fibrous structure comprises filaments having one or more filament-forming materials and one or more active agents releasable from the filaments upon exposure to conditions of intended use. The fibrous structure further comprises a continuous network region and a plurality of discrete zones. The continuous network region comprises a first average density and the plurality of discrete regions comprises a second average density. The discrete regions are dispersed throughout the network area and the first and second average densities are different.

According to another embodiment, a fibrous structure comprises filaments having one or more filament-forming materials and one or more active agents that are releasable from the filaments upon exposure to conditions of intended use. The fibrous structure further comprises at least a first region and a second region. Each of the first and second regions has at least one common intensity characteristic. The at least one common intensity characteristic of the first region differs in value from the at least one common intensity characteristic of the second region.

According to another embodiment, a method for making a fibrous structure is provided. The method comprises the following steps: depositing a plurality of filaments onto a three-dimensional molding member comprising a non-random repeating pattern such that a fibrous structure comprising one or more filament-forming materials and one or more active agents releasable from the filaments upon exposure to conditions of intended use is produced. The fibrous structure further comprises at least a first region and a second region. Each of the first and second regions has at least one common intensity characteristic. The at least one common intensity characteristic of the first region differs in value from the at least one common intensity characteristic of the second region.

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be more fully understood from the following description.

Drawings

FIG. 1 is a known nonwoven substrate.

FIG. 2 is another known nonwoven substrate.

Fig. 3 is a schematic plan view of a portion of a fibrous structure.

FIG. 4 is a schematic cross-sectional view of a portion of the fibrous structure shown in FIG. 3, as taken along line 4-4.

FIG. 5 is a schematic plan view of one embodiment of a fibrous structure.

Fig. 6 is a schematic cross-sectional view of fig. 5 taken along line 6-6.

FIG. 7 is a schematic view of an apparatus for forming a fibrous structure.

Fig. 8 is a schematic view of a mold for the apparatus shown in fig. 7.

Fig. 9 is a schematic view of a molding member.

Fig. 10 shows a schematic view of the molding member and the resulting fiber structure.

Fig. 11A is a schematic view of an apparatus for measuring dissolution of a fibrous structure.

Fig. 11B is a schematic top view of fig. 11A.

Fig. 12 is a schematic view of an apparatus for measuring dissolution of a fibrous structure.

Fig. 13 is a cross-sectional view of a network region and a plurality of discrete regions of a fibrous structure as shown using SEM micrographs.

Fig. 14 shows a processed topographical feature image of a network region and a plurality of discrete regions of a fibrous structure as shown using SEM micrographs.

Fig. 15 shows a series of rectilinear regions of interest drawn across the network region and discrete areas shown in fig. 14.

FIG. 16 is a graph showing a height profile from a topographical image along a straight line region of interest, illustrating a plurality of height difference measurements.

FIG. 17 shows a height profile plotted by a topographical image along a straight line region of interest to illustrate a plurality of transition region widths.

Detailed Description

I. Definition of

As used herein, the following terms shall have the meanings specified below:

as used herein, "filament" or "fiber" or "fibrous element" refers to an elongated particle having a length that substantially exceeds its diameter, i.e., having a length to diameter ratio of at least about 10. The fibrous elements may be filaments or fibers. In one example, the fiber elements are individual fiber elements rather than yarns comprising multiple fiber elements. The fibrous element may be spun from the filament-forming composition, also referred to as a fibrous element-forming composition, via a suitable spinning operation, such as a melt-blowing process and/or a spunbonding process. The fibrous elements may be monocomponent and/or multicomponent. For example, the fibrous elements may comprise bicomponent fibers and/or filaments. The bicomponent fibers and/or filaments can be in any form, such as side-by-side, core-sheath, islands-in-the-sea, and the like.

As used herein, "filament-forming composition" refers to a composition suitable for making filaments, such as by a melt-blowing process and/or a spunbond process. The filament-forming composition comprises one or more filament-forming materials that exhibit properties that make them suitable for spinning into filaments. In one example, the filament-forming material comprises a polymer. The filament-forming composition may further comprise one or more additives, such as one or more active agents, in addition to the one or more filament-forming materials. In addition, the filament-forming composition may comprise one or more polar solvents, such as water, in which one or more (e.g., all) of the filament-forming materials and/or one or more (e.g., all) of the active agents are dissolved and/or dispersed.

As used herein, "filament-forming material" refers to a material, such as a polymer or a monomer capable of producing a polymer, that exhibits properties suitable for making a filament. In one example, the filament-forming material comprises one or more substituted polymers such as anionic, cationic, zwitterionic, and/or nonionic polymers. In another example, the polymer can include a hydroxyl polymer, such as polyvinyl alcohol ("PVOH"), and/or a polysaccharide, such as starch, and/or a starch derivative, such as ethoxylated starch, and/or acid hydrolyzed starch. In another example, the polymer may comprise polyethylene and/or terephthalic acid. In another example, the filament-forming material is a polar solvent soluble material.

As used herein, "additive" refers to any material present in the filament that is not a filament-forming material. In one example, the additive includes an active agent. In another example, the additive comprises a processing aid. In another example, the additive includes a filler. In one example, the additive includes any material present in the filament that, if absent from the filament, would not cause the filament to lose its filament structure, in other words, its absence would not cause the filament to lose its solid form. In another example, the additive, such as an active agent, includes a non-polymeric material.

As used herein, "conditions of intended use" refers to the temperature, physical, chemical, and/or mechanical conditions to which the filament is exposed when it is used in one or more of its intended uses. For example, if the filaments and/or nonwoven web comprising filaments are designed for laundry care purposes in a laundry washing machine, the expected use conditions will include those temperature, chemical, physical and/or mechanical conditions present in the laundry washing machine during a laundry washing operation, including any wash water. In another example, if the filaments and/or nonwoven web comprising filaments are designed for use in a shampoo for human hair care purposes, the intended use conditions will include those temperature, chemical, physical and/or mechanical conditions that exist during shampooing of human hair. Likewise, if the filaments and/or nonwoven webs comprising filaments are designed for hand dishwashing or dishwasher dishwashing, the expected conditions of use will include those temperature, chemical, physical and/or mechanical conditions present in the dishwashing water and/or dishwasher during a dishwashing operation.

As used herein, "active agent" refers to an additive that produces the desired effect on the filaments and/or nonwoven webs comprising the filaments of the present invention in an external environment, for example when the filaments are exposed to the conditions of intended use of the filaments and/or nonwoven webs comprising the filaments. In one example, the active agent includes an additive that treats a surface such as a hard surface (i.e., kitchen countertops, bathtubs, toilets, sinks, floors, walls, teeth, automobiles, windows, mirrors, dishes) and/or a soft surface (i.e., fabrics, hair, skin, carpets, crops, plants'). In another example, the active agent includes an additive that produces a chemical reaction (i.e., a chemical reaction in clarified and/or disinfected and/or chlorinated water, for example), foaming, bubbling, coloring, warming, cooling, frothing, disinfecting, and/or clarifying and/or chlorinating. In another example, the active agent includes an additive that treats the environment (i.e., deodorizes, purifies, scents the air). In one example, the active agent is formed in situ, e.g., during the formation of a filament comprising the active agent, e.g., the filament can comprise a water soluble polymer (e.g., starch) and a surfactant (e.g., an anionic surfactant), which can create a polymer complex or aggregate that acts as an active agent for treating the surface of the fabric.

As used herein, "fabric care active" refers to an active that provides a benefit and/or improves fabric when applied to fabric. Non-limiting examples of benefits and/or improvements to fabrics include cleaning (e.g., by surfactants), stain removal, stain reduction, de-wrinkling, color restoration, static control, anti-wrinkle, durable press, wear reduction, abrasion protection, pilling/pill removal, anti-pilling/pill, soil release, soil control (including soil release), shape retention, shrinkage reduction, softness, fragrance, antimicrobial, antiviral, anti-odor, and odor removal.

As used herein, "dishwashing active" refers to an active that provides benefits and/or improvements to dishes, glassware, pots, dishes, and/or cooking plates when applied to the dishes, glassware, plastic articles, pots, plates, utensils, and/or cooking plates. Non-limiting examples of benefits and/or improvements to dishes, glassware, plastic articles, pots, plates, utensils, and/or cooking plates include food and/or soil removal, cleaning (e.g., by surfactant cleaning), stain removal, stain reduction, grease removal, scale removal and/or prevention, glass and metal care, disinfection, shine, and polishing.

As used herein, "hard surfactant" refers to an active that provides a benefit and/or improvement to a floor, countertop, sink, window, mirror, shower, bath, and/or toilet when applied to the floor, countertop, sink, window, mirror, shower, bath, and/or toilet. Non-limiting examples of benefits and/or improvements to floors, countertops, sinks, windows, mirrors, showers, bathtubs, and/or toilets include removing food and/or dirt, cleaning (e.g., by surfactants), removing stains, reducing stains, removing grease, removing and/or preventing water stains, removing scale, disinfecting, brightening, polishing, and freshening.

As used herein, "weight ratio" refers to the ratio of the weight of formed material in the filament (g or%) on a dry filament basis and/or on a dry detergent product basis to the weight of one or more additives in the filament (g or%) on a dry weight basis, such as an active agent.

As used herein, "hydroxyl polymer" includes any hydroxyl-containing polymer that can be incorporated into a filament, for example as a filament-forming material. In one example, the hydroxyl polymer comprises greater than 10%, and/or greater than 20%, and/or greater than 25% by weight hydroxyl moieties.

As used herein, "biodegradable" with respect to a material such as a filament as a whole and/or a polymer within a filament such as a filament-forming material means that the filament and/or polymer is capable of and/or does undergo physical, chemical, thermal and/or biological degradation in a municipal solid waste composting plant such that at least 5%, and/or at least 7%, and/or at least 10% of the original filaments and/or polymers are converted to carbon dioxide after 30 days according to OECD (1992) guidelines for the testing of Chemicals 301B; ready Biodegradability-CO₂Evolution (modified SturmTest) Test, which is incorporated herein by reference.

As used herein, "non-biodegradable" with respect to a material, such as filament monoliths, and/or polymers within filaments, such as filament-forming materials, means that the filaments and/or polymers are not capable of physical, chemical, thermal, and/or biological degradation in a municipal solid waste composting plant, such that at least 5% of the original filaments and/or polymers are converted to carbon dioxide after 30 days,this is done according to OECD (1992) guidelines for the Testing of Chemicals 301B; ready Biodegradability-CO₂Evolution (modified Sturm Test) Test, which is incorporated herein by reference.

As used herein, "non-thermoplastic" with respect to a material, such as a polymer, e.g., a filament-forming material, throughout and/or within a filament, means that the filament and/or polymer exhibits no melting and/or softening point, which allows it to flow under pressure in the absence of a plasticizer, such as water, glycerin, sorbitol, urea, and the like.

As used herein, "non-thermoplastic, biodegradable filament" refers to a filament that exhibits the biodegradable and non-thermoplastic properties described above.

As used herein, "non-thermoplastic, non-biodegradable filament" refers to a filament that exhibits the non-biodegradable and non-thermoplastic characteristics described above.

As used herein, "thermoplastic" with respect to a material, such as a polymer, e.g., a filament-forming material, throughout and/or within a filament means that the filament and/or polymer exhibits a melting and/or softening point at a temperature that allows it to flow under pressure in the absence of a plasticizer.

As used herein, "thermoplastic, biodegradable filament" refers to a filament that exhibits the biodegradable and thermoplastic properties described above.

As used herein, "thermoplastic, non-biodegradable filament" refers to a filament that exhibits the non-biodegradable and thermoplastic characteristics described above.

As used herein, "polar solvent-soluble material" refers to a material that is miscible in a polar solvent. In one example, the polar solvent soluble material is miscible in alcohol and/or water. In other words, a polar solvent soluble material is a material that is capable of forming a stable (no phase separation occurs after more than 5 minutes of forming a homogeneous solution) homogeneous solution with a polar solvent such as alcohol and/or water under ambient conditions.

As used herein, "alcohol-soluble material" refers to a material that is miscible in alcohol. In other words, it is a material that is capable of forming a stable (no phase separation occurs after more than 5 minutes of forming a homogeneous solution) homogeneous solution with alcohol under ambient conditions.

As used herein, "water-soluble material" refers to a material that is miscible in water. In other words, it is a material that is capable of forming a stable (no separation occurs more than 5 minutes after forming a homogeneous solution) homogeneous solution with water under ambient conditions.

As used herein, "non-polar solvent soluble material" refers to a material that is miscible in a non-polar solvent. In other words, the nonpolar solvent-soluble material is a material capable of forming a stable (no phase separation occurs after more than 5 minutes from the formation of a homogeneous solution) homogeneous solution with a nonpolar solvent.

As used herein, "ambient conditions" refers to 73 ℉. + -4 deg.F (about 23 deg.C. + -2.2 deg.C.) and 50% + -10% relative humidity.

As used herein, "weight average molecular weight" refers to weight average molecular weight as determined by gel permeation chromatography in accordance with the protocol presented in Colloids and surfaces A. Physico Chemical & Engineering industries, Vol.162, 2000, pp.107 to 121.

As used herein, "length" for a filament refers to the length along the filament from one end to the other. The length is the length along the complete path of the filament if there are knots, crimps or bends in the filament.

As used herein, "diameter" is measured for a filament according to the diameter test method described herein. In one example, the filaments may exhibit a diameter of less than 100 μm, and/or less than 75 μm, and/or less than 50 μm, and/or less than 25 μm, and/or less than 20 μm, and/or less than 15 μm, and/or less than 10 μm, and/or less than 6 μm, and/or greater than 1 μm, and/or greater than 3 μm.

As used herein, "trigger condition" refers in one example to any action or event for stimulating or initiating or causing a change in the filament, such as loss or changing the physical structure of the filament and/or releasing an additive such as an active agent. In another example, the trigger condition may be present in the environment, for example, when the filaments and/or nonwoven web and/or film are added to water. In other words, no change in water occurs other than the fact that the filaments, and/or nonwoven web, and/or film are added to the water.

As used herein, "morphological change" with respect to a morphological change of a filament means that the filament undergoes a change in its physical structure. Non-limiting examples of morphological changes to the filaments include dissolution, melting, swelling, crimping, fragmentation into segments, expansion, lengthening, shortening, and combinations thereof. The filaments may completely or substantially lose their filament physical structure or they may undergo a morphological change or they may retain or substantially retain their filament physical structure when exposed to conditions of intended use.

As used herein, "total content" with respect to the total content of one or more active agents, e.g., present in a filament and/or dry detergent product, refers to the total weight or total weight% of all tested materials, e.g., active agents. In other words, the filament and/or detergent product may comprise 25% anionic surfactant on a dry filament basis and/or by weight of the dry detergent product, 15% nonionic surfactant on a dry filament basis and/or by weight of the dry detergent product, 10% by weight of the chelating agent, and 5% perfume, whereby the total level of active present in the filament is greater than 50%; i.e. 55% by weight on dry filaments and/or on dry detergent product.

As used herein, "detergent product" refers to a solid form, e.g., a rectangular solid, sometimes referred to as a tablet, that contains one or more actives, e.g., fabric care actives, dishwashing actives, hard surfactants, and mixtures thereof. In one example, the detergent product may comprise one or more surfactants, one or more enzymes, one or more perfumes, and/or one or more suds suppressors. As another example, the detergent product may comprise a builder and/or a chelant. As another example, the detergent product may comprise a bleaching agent.

As used herein, "web" refers to a collection of fibers and/or filaments of any nature or origin that are associated with one another, such as a fibrous structure, and/or a detergent product of fibers, and/or filaments, such as continuous filaments. In one example, the web is a rectangular solid comprising fibers and/or filaments formed via a spinning process rather than a casting process.

For purposes of this disclosure, "nonwoven web" as used herein and generally defined by the European Disposables and nowovins association (EDANA) refers to a sheet of fibers and/or filaments of any nature or origin, such as continuous filaments, that have been formed into a web by any means, and may be joined together by any means other than weaving or knitting. The felt obtained by wet milling is not a nonwoven web. In one example, a nonwoven web refers to an ordered arrangement of functional-performing filaments in a structure. In one example, the nonwoven web is an arrangement comprising groups of two or more and/or three or more filaments that are intertwined or otherwise associated with each other to form the nonwoven web. In one example, the nonwoven web may contain one or more solid additives, such as particles and/or fibers, in addition to the filaments.

As used herein, "granules" refers to granular materials and/or powders. In one example, the filaments and/or fibers may be converted to a powder.

As used herein, "equivalent diameter" defines the cross-sectional area and surface area of an individual starch filament regardless of the cross-sectional shape. The equivalent diameter satisfies the formula S-1/4 pi D²Where S is the cross-sectional area of the filament (irrespective of its geometry), pi 3.14159 and D is the equivalent diameter. For example, having two mutually opposed sides "A" and two mutually opposed sidesThe cross-section of the rectangular shape formed by the opposing sides "B" can be expressed as: s ═ a × B. Meanwhile, the cross-sectional area may be expressed as a circular area having an equivalent diameter D. Then, the equivalent diameter D can be calculated by the following formula: s-1/4 pi D²Where S is the known area of the rectangle. (of course, the equivalent diameter of a circle is the actual diameter of a circle). The equivalent radius is 1/2 of the equivalent diameter.

"pseudo thermoplastic" in combination with "material" or "composition" is intended to mean the following materials and compositions: are subjected to elevated temperatures, are dissolved in a suitable solvent, or otherwise can be softened to such an extent that they can be brought into a flowable state, under which conditions they can be formed into the desired, and more specifically, processed to form starch filaments suitable for forming into fibrous structures. The pseudo thermoplastic material may be formed, for example, under the combined influence of heat and pressure. Pseudo thermoplastic materials are distinguished from thermoplastic materials in that the softening or liquefaction of the pseudo thermoplastic material is formed in the presence of a softening or solvent, without which it would not be possible to bring them into the softened or flowable condition necessary for forming by any temperature or pressure, since the pseudo thermoplastic material itself does not "melt". The effect of water content on the glass transition temperature and melting temperature of starch can be measured by differential scanning calorimetry as described by Zeleznak and Hoseny in "Cereal Chemistry", volume 64, phase 2, pages 121-. The pseudo thermoplastic melt is a pseudo thermoplastic material in a flowable state.

"microscopic geometry" and its arrangement refer to the relatively small (i.e., "microscopic") details of a fibrous structure, such as surface texture, relative to its overall (i.e., "macroscopic") geometry, regardless of the overall configuration of the structure. Terms comprising "macroscopic" or "macroscopically" refer to the overall geometry of a structure or a portion thereof under consideration when placed in a two-dimensional configuration, such as an X-Y plane. For example, on a macroscopic level, a fibrous structure comprises a relatively thin and flat sheet when it is disposed on a flat surface. However, on a macroscopic level, the structure may include a plurality of first regions forming a first plane having a first height, and a plurality of "domes" or "pillows" dispersed throughout and extending outwardly from the frame region to form a second height.

"strength properties" are properties that do not have values that depend on a set of values within the plane of the fibrous structure. A common intensity characteristic is an intensity characteristic that is possessed by more than one region. Such strength characteristics of the fibrous structure include, but are not limited to, density, basis weight, height, and opacity. For example, if the density is a common intensity characteristic of two different regions, the density value in one region may be different from the density value in the other region. The regions (such as the first region and the second region) are identifiable regions that are distinguishable from each other by different intensity characteristics.

"glass transition temperature", T_gIs the temperature at which the material changes from a viscous or rubbery state to a hard and relatively brittle state.

The "machine direction" (or MD) is the direction parallel to the flow of the fibrous structure being produced by the manufacturing apparatus. The "cross direction" (or CD) is the direction perpendicular to the machine direction and parallel to the general plane of the fibrous structure being prepared.

"X", "Y", and "Z" designate a conventional system of Cartesian coordinates (Cartesian coordinates) in which the mutually perpendicular coordinates "X" and "Y" define a reference X-Y plane, and "Z" defines an orthogonal plane to the X-Y plane. The "Z direction" is named for any direction perpendicular to the X-Y plane. Similarly, the term "Z dimension" refers to a dimension, distance, or parameter measured parallel to the Z direction. The X-Y plane conforms to the configuration of an element, such as a molding member, when the element is bent or otherwise non-planar.

A "substantially continuous" region is a region in which any two points may be connected by an uninterrupted line, the entire line length of which runs entirely within the region. That is, the substantially continuous region has a substantial "continuity" in all directions parallel to the first plane and terminates only at the edges of said region. In connection with "continuous", the term "substantially" is intended to mean that while absolute continuity is preferred, minor deviations from absolute continuity are also tolerable, provided that such deviations do not significantly affect the properties for which the fibrous structure (or molding member) is designed and intended.

A "substantially semi-continuous" region is a region that has "continuity" in all but at least one direction parallel to the first plane and in which any two points cannot be connected by an unbroken line whose entire line length runs entirely within the region. The semi-continuous frame may have continuity in only one direction parallel to the first plane. Similar to the continuous regions described above, although absolute continuity in all but at least one direction is preferred, minor deviations from this continuity are also tolerable, as long as these deviations do not significantly affect the properties of the fibrous structure.

By "discontinuous" regions are meant discrete and spaced apart regions that are discontinuous in all directions parallel to the first plane.

"flexibility" is the ability of a material or structure to deform without breaking under a given load, regardless of the ability of the material or structure to be able or unable to return itself to its pre-deformed shape.

A "molding member" is a structural element that can be used as a carrier on which filaments can be deposited during the process of making a fibrous structure and can be used as a forming unit to form (or "mold") the desired micro-geometry of the fibrous structure. The molding member may comprise any element having the ability to impart a three-dimensional pattern to the structure produced thereon, and includes, but is not limited to, a holding plate, a belt, a cylinder/roll, a woven fabric, and a belt.

"melt spinning" is a process whereby a thermoplastic or pseudo thermoplastic material is converted into a fibrous material by using a drawing force. Melt spinning can include mechanical elongation, melt blowing, spunbonding, and electrospinning.

"mechanical elongation" is a process by which a fiber is made by directing a force onto a fiber strand by contacting the fiber strand with a driven surface, such as a roller, thereby applying the force to the melt.

"meltblown" is a process in which a web or article is made directly from a polymer or resin by attenuating the filaments with high velocity air or another suitable force. In the melt blowing process, the drawing force is applied as high velocity air as the material exits the die or spinneret.

"spunbonding" includes the process of dropping fibers a predetermined distance under the force of flow and gravity, then applying force via high velocity air or another suitable source.

"electrospinning" is a process that uses an electrical potential as a means to attenuate a fiber.

"dry spinning," also often referred to as "solution spinning," involves the use of solvent drying to stabilize the fiber formation. The material is dissolved in a suitable solvent and attenuated via mechanical elongation, melt blowing, spunbonding, and/or electrospinning. As the solvent evaporates, the fiber becomes stable.

"wet spinning" includes dissolving a material in a suitable solvent and forming fibrils via mechanical stretching, melt blowing, spunbonding, and/or electrospinning. As the fiber is formed, it enters a coagulation system, which typically includes a bath filled with a suitable solution that solidifies the desired material, thereby producing a stable fiber.

"melting temperature" refers to a temperature or temperature range at or above which the starch composition melts or softens sufficiently to be able to be processed into starch filaments. It should be understood that some starch compositions are pseudo-thermoplastic compositions and may not exhibit pure "melting" behavior by themselves.

"processing temperature" refers to the temperature of the starch composition at which starch filaments can be formed, for example, by attenuation.

As used herein, "basis weight" is the weight per unit area of a sample, recorded in gsm, and measured according to the basis weight test method described herein.

As used herein, "fibrous structure" refers to a structure comprising one or more fiber filaments and/or fibers. In one example, a fibrous structure refers to an ordered arrangement of filaments and/or fibers in a structure in order to perform a function. Non-limiting examples of fibrous structures may include detergent products, fabrics (including woven, knitted, and nonwoven), and absorbent pads (e.g., for diapers or feminine hygiene articles). The fibrous structures of the present invention may be uniform or may be layered. If layered, the fibrous structure may comprise at least two, and/or at least three, and/or at least four, and/or at least five layers, such as one or more layers of fibrous elements, one or more layers of particles, and/or one or more layers of fibrous element/particle mixtures.

The articles "a" and "an" as used herein, such as "an anionic surfactant" or "a fiber," are understood to mean one or more of what is claimed or described.

All percentages and ratios are by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition, unless otherwise indicated.

Unless otherwise indicated, all component or composition levels are in reference to the active level of that component or composition, and are exclusive of impurities, e.g., residual solvents or by-products, which may be present in commercially available sources.

Fiber Structure

As shown in fig. 3-4, the fibrous structure 20 may be formed from filaments having at least a first region (e.g., network region 22) and a second region (e.g., discrete region 24). Each of the first and second regions has at least one common strength characteristic, such as basis weight or average density. The common intensity characteristic of the first region may differ in value from the common intensity characteristic of the second region. For example, the average density of the first region may be higher than the average density of the second region. Fig. 3 shows a plan view of a portion of the fibrous structure 20 with the network regions 22 shown in the form of defined hexagons, but it should be understood that other preselected patterns may be used.

Fig. 4 is a cross-sectional view of the fibrous structure 20 of fig. 3 taken along line 4-4. As can be seen from the embodiment shown in fig. 4, the network area 22 is substantially monoplanar. In one example, the network region is a macroscopically monoplanar, patterned, continuous network region. The second region of the fibrous structure 20 may comprise a plurality of discrete regions 24 distributed throughout the network region 22 and substantially each surrounded by the network region 22. The shape of the discrete areas 24 may be defined by the network region 22. As shown in fig. 4, the discrete areas 24 appear to extend (project) from the plane formed by the network area 22 toward an imaginary observer viewed in the direction of arrow T. The second region includes an arcuate void that appears as a cavity or recess when viewed by an imaginary observer looking in the direction indicated by arrow B in fig. 4.

As shown in another embodiment of fig. 5-6, the first and second regions 122 and 124 of the fibrous structure 120 may also differ in their respective micro-geometries. In fig. 5-6, for example, the first region 122 comprises a substantially continuous network that forms a first plane at a first height when the fibrous structure 120 is disposed on a flat surface; and the second region 124 may comprise a plurality of discrete zones dispersed throughout a substantially continuous network. In some embodiments, these discrete regions may comprise discrete protrusions or "pillows" that extend outwardly from the network area to form a second height relative to the first plane that is greater than the first height. It should be understood that the pillows may also comprise a substantially continuous pattern and a substantially semi-continuous pattern.

In one embodiment, the substantially continuous network region may have a relatively high density and the pillows have a relatively low density. In other embodiments, the substantially continuous network region may have a relatively low density and the pillows may have a relatively high density. In certain embodiments, the fibrous structure may exhibit a basis weight of about 3000gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 1500gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 1000gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 700gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 500gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 300gsm or less; in certain embodiments, the fibrous structure may exhibit a basis weight of about 200gsm or less; and in certain embodiments, the fibrous structure may exhibit a basis weight of about 150 or less as measured according to the basis weight test method described herein.

In other embodiments, the second area may comprise a semi-continuous network. The second region may comprise discrete regions similar to those shown in fig. 5-6; and semi-discrete regions extending in at least one direction as seen in the X-Y plane (i.e., the plane formed by the first regions 122 of the fibrous structure 120 disposed on a flat surface).

In the embodiment shown in fig. 5 and 6, the fibrous structure 120 includes a third region 130 having at least one strength characteristic that is common to and different in value from the strength characteristics of the first region 122 and the strength characteristics of the second region 124. For example, the first region 122 may include a common intensity characteristic having a first value, the second region 124 may include a common intensity characteristic having a second value, and the third region 130 may include a common intensity characteristic having a third value, wherein the first value may be different from the second value, and the third value may be different from the second value and the first value. In one embodiment, such third regions may include a transition region 135 (see fig. 4) located between the first region 122 and the second region 124. The transition region 135 is the region between which the network region and the discrete region transition.

As described herein, when the fibrous structure 120 comprising at least three distinct regions 122, 124, 130 is disposed on a horizontal reference plane (e.g., an X-Y plane), the first region 122 defines a plane having a first height and the second region 124 extends therefrom to define a second height. An embodiment is contemplated wherein the third region 130 defines a third height, wherein at least one of the first height, the second height, and the third height is different from at least one of the other heights. For example, the third height may be intermediate the first height and the second height.

A suitable fibrous structure having a network of regions and a plurality of discrete regions may have a predetermined height. For example, in certain embodiments, one of the network regions or discrete regions has a height of about 50 microns at least about 5000 microns; for example, in certain embodiments, one of the network regions or discrete regions may have a height of about 100 microns to about 2000 microns; and in certain embodiments, one of the network regions or discrete regions has a height of about 150 microns to about 1500 microns.

The following table illustrates, without limitation, some possible combinations of embodiments of the fibrous structure 120 comprising at least three regions having different (e.g., high, medium, or low) strength characteristics. All such embodiments are included within the scope of the present disclosure.

As described herein, suitable fibrous structures may comprise network regions and discrete regions having different (e.g., non-identical) average densities. The average density of any one network region or discrete region may be from about 0.05g/cc to about 0.80g/cc, in certain embodiments from about 0.10g/cc to about 0.50g/cc, and in certain embodiments, from about 0.15g/cc to about 0.40 g/cc. In other embodiments, the network region may have an average density of about 0.05g/cc to about 0.15g/cc and the discrete regions may have an average density of about 0.15g/cc to about 0.80 g/cc; alternatively, the network region may have an average density of about 0.07g/cc to about 0.13g/cc and the discrete regions may have an average density of about 0.25g/cc to about 0.70 g/cc; alternatively, the network region may have an average density of about 0.08g/cc to about 0.12g/cc and the discrete regions may have an average density of about 0.40g/cc to about 0.60 g/cc. In other certain embodiments, the average density values are vice versa for each network region and discrete area. The ratio of the average density of the network region to the average density of the discrete zones may be greater than 1, taking into account the number of fibers per unit area projected onto the portion of the fibrous structure under consideration. In another embodiment, the ratio of the average density of the network region to the average density of the discrete regions may be less than 1.

In certain embodiments, the ratio of the basis weight of the network region to the basis weight of the discrete regions is from about 0.5 to about 1.5; and in certain embodiments, the ratio of the basis weight of the network regions to the basis weight of the discrete regions is from about 0.8 to about 1.2.

In certain embodiments, the network region may comprise from about 5% to about 95% of the total area of the fibrous structure; and in certain embodiments, from about 20% to about 40% of the total area of the fibrous structure. In certain embodiments, the plurality of discrete regions may comprise from about 5% to about 95% of the total area of the fibrous structure; and in certain embodiments, from about 60% to about 80% of the total area of the fibrous structure.

In certain embodiments, suitable fibrous structures may have a water content (moisture%) of 0% to about 20%; in certain embodiments, the fibrous structure may have a water content of from about 1% to about 15%; and in certain embodiments, the fibrous structure may have a water content of from about 5% to about 10%.

In certain embodiments, a suitable fibrous structure may exhibit a tensile test method according to the tensile test methods described herein of about 100g in/in²Or greater, and/or about 150g in/in²Or greater, and/or about 200g in/in²Or greater, and/or about 300g in/in²Or a larger geometric mean TEA.

In certain embodiments, suitable fibrous structures may exhibit a geometric mean modulus according to the tensile test method described herein of about 5000g/cm or less, and/or 4000g/cm or less, and/or about 3500g/cm or less, and/or about 3000g/cm or less, and/or about 2700g/cm or less.

In certain embodiments, suitable fibrous structures as described herein can exhibit a geometric mean peak elongation of about 10% or greater, and/or about 20% or greater, and/or about 30% or greater, and/or about 50% or greater, and/or about 60% or greater, and/or about 65% or greater, and/or about 70% or greater, as measured according to the tensile test method.

In certain embodiments, suitable fibrous structures as described herein may exhibit a geometric mean tensile strength of about 200g/in or greater, and/or about 300g/in or greater, and/or about 400g/in or greater, and/or about 500g/in or greater, and/or about 600g/in or greater, as measured according to the tensile test method described herein.

Other suitable fiber structure arrangements are described in U.S. Pat. No. 4,637,859 and U.S. patent application publication 2003/0203196.

Additionally, non-limiting examples of other suitable fibrous structures are disclosed in U.S. provisional patent application 61/583,018(P & G attorney docket No. 12330P), filed concurrently with the present application and incorporated herein by reference.

The use of such fibrous structures as described herein as detergent products provides benefits beyond the prior art. By including at least two regions within the fibrous structure having different strength characteristics, the fibrous structure may provide sufficient integrity prior to use, but during use (e.g., in a washing machine), the fibrous structure may sufficiently dissolve and release the active agent. Furthermore, such fibrous structures are non-tacky to any article being laundered (e.g., clothes) or to the surface of a washing machine, and such fibrous structures will not clog the drainage cells of the washing machine.

A. Filament yarn

The filaments may comprise one or more filament-forming materials. The filament may further comprise one or more active agents in addition to the filament-forming material, for example the active agents are releasable from the filament when the filament is exposed to conditions of intended use, wherein the total level of the one or more filament-forming materials present in the filament is less than 80% by weight on a dry filament basis and/or based on the weight of a dry detergent product, and the total level of the one or more active agents present in the filament is greater than 20% by weight on a dry filament basis and/or based on the weight of a dry detergent product.

In another example, the filaments may comprise one or more filament-forming materials and one or more active agents, wherein the total level of filament-forming materials present in the filaments may be from about 5% to less than 80% by weight on a dry filament basis and/or on a dry detergent product basis, and the total level of active agents present in the filaments may be from greater than 20% to about 95% by weight on a dry filament basis and/or on a dry detergent product basis.

In one example, the filaments may comprise at least 10%, and/or at least 15%, and/or at least 20%, and/or less than 80%, and/or less than 75%, and/or less than 65%, and/or less than 60%, and/or less than 55%, and/or less than 50%, and/or less than 45%, and/or less than 40% of the filament-forming material on a dry filament basis and/or based on the weight of the dry detergent product, and greater than 20%, and/or at least 35%, and/or at least 40%, and/or at least 45%, and/or at least 50%, and/or at least 60%, and/or less than 95%, and/or less than 90%, and/or less than 85% on a dry filament basis and/or based on the weight of the dry detergent product, And/or less than 80%, and/or less than 75% active agent.

In one example, the filaments may comprise at least 5%, and/or at least 10%, and/or at least 15%, and/or at least 20%, and/or less than 50%, and/or less than 45%, and/or less than 40%, and/or less than 35%, and/or less than 30%, and/or less than 25% of the filament-forming material on a dry filament basis and/or by weight of the dry detergent product, and greater than 50%, and/or at least 55%, and/or at least 60%, and/or at least 65%, and/or at least 70%, and/or less than 95%, and/or less than 90%, and/or less than 85%, and/or less than 80%, and/or less than 75% active agent by weight of the dry filament and/or based on the dry detergent product. In one example, the filaments may comprise greater than 80% active agent by weight of the dry filaments and/or on a dry detergent product.

In another example, the one or more filament-forming materials and active agent are present in the filament at a weight ratio of the total content of filament-forming materials to the total content of active agent of 4.0 or less, and/or 3.5 or less, and/or 3.0 or less, and/or 2.5 or less, and/or 2.0 or less, and/or 1.85 or less, and/or less than 1.7, and/or less than 1.6, and/or less than 1.5, and/or less than 1.3, and/or less than 1.2, and/or less than 1, and/or less than 0.7, and/or less than 0.5, and/or less than 0.4, and/or less than 0.3, and/or greater than 0.1, and/or greater than 0.15, and/or greater than 0.2.

In another example, the filaments may comprise from about 10% and/or from about 15% to less than 80% of a filament-forming material, such as a polyvinyl alcohol polymer and/or a starch polymer, on a dry filament basis and/or by weight of the dry detergent product, and from greater than 20% to about 90% and/or to about 85% of an active agent, on a dry filament basis and/or by weight of the dry detergent product. The filaments may also comprise a plasticizer such as glycerin and/or a pH adjuster such as citric acid.

In another example, the filaments may comprise from about 10% and/or from about 15% to less than 80% filament-forming material, such as polyvinyl alcohol polymer and/or starch polymer, on a dry filament basis and/or by weight of the dry detergent product, and from greater than 20% to about 90% and/or to about 85% active agent, on a dry filament basis and/or by weight of the dry detergent product, wherein the weight ratio of filament-forming material to active agent is 4.0 or less. The filaments may also comprise a plasticizer such as glycerin and/or a pH adjuster such as citric acid.

In even another example, the filaments may comprise one or more filament-forming materials and one or more active agents selected from the group consisting of: enzymes, bleaches, builders, chelating agents, sensates, dispersants, and mixtures thereof, which are releasable and/or released from the filaments when the filaments are exposed to conditions of intended use. In one example, the filaments comprise a total content of filament-forming material of less than 95%, and/or less than 90%, and/or less than 80%, and/or less than 50%, and/or less than 35%, and/or to about 5%, and/or to about 10%, and/or to about 20%, based on the dry filaments and/or based on the amount of dry detergent product, and a total content of active agent of greater than 5%, and/or greater than 10%, and/or greater than 20%, and/or greater than 35%, and/or greater than 50%, and/or greater than 65%, and/or to about 95%, and/or to about 90%, and/or to about 80%, based on the weight of the dry filaments and/or based on the weight of the dry detergent product, the active agent being selected from the group consisting of: enzymes, bleaches, builders, chelating agents, and mixtures thereof. In one example, the active agent includes one or more enzymes. In another example, the active agent includes one or more bleaching agents. In another example, the active agent includes one or more builders. In another example, the active agent includes one or more chelating agents.

In another example, the filaments may contain active agents that may create health and/or safety issues if become airborne. For example, the filaments may be used to inhibit enzymes within the filaments from becoming airborne.

In one example, the filaments may be meltblown filaments. In another example, the filaments may be spunbond filaments. In another example, the filament may be a hollow filament before and/or after release of one or more of its active agents.

Suitable filaments may be hydrophilic or hydrophobic. The filaments may be surface treated and/or internally treated to alter the inherent hydrophilic or hydrophobic properties of the filaments.

In one example, the filaments exhibit a diameter of less than 100 μm, and/or less than 75 μm, and/or less than 50 μm, and/or less than 30 μm, and/or less than 10 μm, and/or less than 5 μm, and/or less than 1 μm, as measured according to the diameter test method described herein. In another example, the filaments may exhibit a diameter of greater than 1 μm as measured according to the diameter test method described herein. The diameter of the filament may be used to control the release rate and/or the depletion rate of one or more active agents present in the filament and/or to alter the physical structure of the filament.

The filament may comprise two or more different active agents. In one example, the filament comprises two or more different active agents, wherein the two or more different active agents are compatible with each other. In another example, the filament can comprise two or more different active agents, wherein the two or more different active agents are incompatible with each other.

In one example, the filament may comprise an active agent within the filament and an active agent on the outer surface of the filament, such as a coating of the filament. The active agent on the outer surface of the filament may be the same or different than the active agent present in the filament. If different, the active agents may or may not be compatible with each other.

In one example, the one or more active agents may be uniformly distributed or substantially uniformly distributed throughout the filament. In another example, one or more active agents may be distributed to discrete regions within the filament. In another example, at least one active agent is distributed uniformly or substantially uniformly throughout the filament, and at least another active agent is distributed as one or more discrete zones within the filament. In another example, at least one active agent is distributed into one or more discrete regions within the filament and at least one other active agent is distributed into one or more discrete regions within the filament different from the first discrete region.

The filaments may be used as discrete articles. In one example, the filaments can be applied to and/or deposited on a carrier substrate, such as a wipe, tissue, toilet tissue, facial tissue, sanitary napkin, tampon, diaper, adult incontinence article, dishwashing cloth, dryer paper, laundry sheet, laundry bar, dry laundry sheet, netting, filter paper, fabric, garment, undergarment, and the like.

In addition, a plurality of filaments can be collected and extruded into a film, thus producing a film comprising one or more filament-forming materials and one or more active agents that can be released from the film, such as when the film is exposed to conditions of intended use.

In one example, a fibrous structure having such filaments can exhibit an average disintegration time of about 60 seconds(s) or less, and/or about 30s or less, and/or about 10s or less, and/or about 5s or less, and/or about 2.0s or less, and/or about 1.5s or less, as measured according to the dissolution test method described herein.

In one example, a fibrous structure having such filaments can exhibit an average dissolution time of about 600 seconds(s) or less, and/or about 400s or less, and/or about 300s or less, and/or about 200s or less, and/or about 175s or less, as measured according to the dissolution test method described herein.

In one example, a fibrous structure having such filaments can exhibit an average disintegration time per gsm sample of about 1.0 seconds per gsm (s/gsm) or less, and/or about 0.5s/gsm or less, and/or about 0.2s/gsm or less, and/or about 0.1s/gsm or less, and/or about 0.05s/gsm or less, and/or about 0.03s/gsm or less, as measured according to the dissolution test method described herein.

In one example, a fibrous structure having such filaments can exhibit an average dissolution time per gsm sample of about 10 seconds per gsm (s/gsm) or less, and/or about 5.0s/gsm or less, and/or about 3.0s/gsm or less, and/or about 2.0s/gsm or less, and/or about 1.8s/gsm or less, and/or about 1.5s/gsm or less, as measured according to the dissolution test method described herein.

B. Filament-forming material

The filament-forming material may comprise any suitable material, such as a polymer exhibiting properties suitable for making filaments, such as by a spinning process, or a monomer capable of making a polymer.

In one example, the filament-forming material may include a polar solvent-soluble material, such as an alcohol-soluble material and/or a water-soluble material.

In another example, the filament-forming material may include a non-polar solvent soluble material.

In another example, the filament-forming material may comprise polar solvent soluble material and be free (less than 5%, and/or less than 3%, and/or less than 1%, and/or 0% by weight of the dry filament and/or dry detergent product) of non-polar solvent soluble material.

In another example, the filament-forming material can be a film-forming material. In another example, the filament-forming material may be of synthetic or natural origin, and it may be chemically, enzymatically, and/or physically altered.

In even another example, the filament-forming material can comprise a polymer selected from the group consisting of: polymers derived from acrylic monomers such as ethylenically unsaturated carboxyl monomers and ethylenically unsaturated monomers, polyvinyl alcohol, polyacrylates, polymethacrylates, copolymers of acrylic acid and methyl acrylate, polyvinylpyrrolidone, polyalkylene oxides, starch and starch derivatives, pullulan, pectin, hydroxypropyl methylcellulose, and carboxymethyl cellulose.

In another example, the filament-forming material may comprise a polymer selected from the group consisting of: polyvinyl alcohol, polyvinyl alcohol derivatives, carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol, starch derivatives, cellulose, hemicellulose derivatives, proteins, sodium alginate, hydroxypropyl methylcellulose, chitosan derivatives, polyethylene glycol, tetramethylene ether glycol, polyvinylpyrrolidone, hydroxymethyl cellulose, hydroxyethyl cellulose, and mixtures thereof.

In another example, the filament-forming material comprises a polymer selected from the group consisting of: pullulan, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, carboxymethyl cellulose, sodium alginate, xanthan gum, tragacanth gum, guar gum, acacia gum, polyacrylic acid, methylmethacrylate copolymer, carboxyvinyl polymer, dextrin, pectin, chitin, levan, elsinan, collagen, pectin, zeatin, gluten, soy protein, casein, polyvinyl alcohol, starch derivatives, hemicellulose derivatives, proteins, chitosan derivatives, polyethylene glycol, tetramethylene ether glycol, hydroxymethyl cellulose, and mixtures thereof.

i.Polar solvent soluble materials

Non-limiting examples of polar solvent-soluble materials include polar solvent-soluble polymers. The polar solvent soluble polymer may be of synthetic or natural origin and may be chemically and/or physically altered. In one example, the polar solvent soluble polymer exhibits a weight average molecular weight of at least 10,000g/mol, and/or at least 20,000g/mol, and/or at least 40,000g/mol, and/or at least 80,000g/mol, and/or at least 100,000g/mol, and/or at least 1,000,000g/mol, and/or at least 3,000,000g/mol, and/or at least 10,000,000g/mol, and/or at least 20,000,000g/mol, and/or to about 40,000,000g/mol, and/or to about 30,000,000 g/mol.

In one example, the polar solvent soluble polymer is selected from: alcohol soluble polymers, water soluble polymers, and mixtures thereof. Non-limiting examples of water-soluble polymers include water-soluble hydroxyl polymers, water-soluble thermoplastic polymers, water-soluble biodegradable polymers, water-soluble non-biodegradable polymers, and mixtures thereof. In one example, the water-soluble polymer includes polyvinyl alcohol. In another example, the water-soluble polymer includes starch. In another example, the water-soluble polymer includes polyvinyl alcohol and starch.

a.Water-soluble hydroxyl polymer

Non-limiting examples of water-soluble hydroxyl polymers can include polyols such as polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch derivatives, starch copolymers, chitosan derivatives, chitosan copolymers, cellulose derivatives such as cellulose ether and cellulose ester derivatives, cellulose copolymers, hemicellulose derivatives, hemicellulose copolymers, gums, arabinans, galactans, proteins and various other polysaccharides, and mixtures thereof.

In one example, the water-soluble hydroxyl polymer can include a polysaccharide.

The term "polysaccharide" as used herein refers to natural polysaccharides and polysaccharide derivatives and/or modified polysaccharides. Suitable water-soluble polysaccharides include, but are not limited to, starch derivatives, chitosan derivatives, cellulose derivatives, hemicellulose derivatives, gums, arabinans, galactans, and mixtures thereof. The water-soluble polysaccharide may exhibit a weight average molecular weight of from about 10,000 to about 40,000,000g/mol, and/or greater than 100,000g/mol, and/or greater than 1,000,000g/mol, and/or greater than 3,000,000 to about 40,000,000 g/mol.

The water-soluble polysaccharide may comprise a non-cellulosic and/or non-cellulosic derivative and/or non-cellulosic copolymer water-soluble polysaccharide. Such non-cellulosic water-soluble polysaccharides may be selected from: starch, starch derivatives, chitosan derivatives, hemicellulose derivatives, gums, arabinans, galactans, and mixtures thereof.

In another example, the water-soluble hydroxyl polymer can include a non-thermoplastic polymer.

The water-soluble hydroxyl polymer can have a weight average molecular weight of from about 10,000g/mol to about 40,000,000g/mol, and/or greater than 100,000g/mol, and/or greater than 1,000,000g/mol, and/or greater than 3,000,000g/mol to about 40,000,000 g/mol. Higher and lower molecular weight water-soluble hydroxyl polymers can be used in combination with hydroxyl polymers having some desired weight average molecular weight.

Such as well-known modifications of water-soluble hydroxyl polymers, e.g. native starch, including chemical and/or enzymatic modifications. For example, native starch may be acid thinned, hydroxyethylated, hydroxypropylated and/or oxidized. In addition, the water-soluble hydroxyl polymer may comprise dent corn starch.

Naturally occurring starches are generally mixtures of amylose and amylopectin polymers of D-glucose units, amylose being essentially a substantially linear polymer of D-glucose units joined by (1,4) - α -D bonds, amylopectin being a highly branched polymer of D-glucose units joined at branch points by (1,4) - α -D bonds and (1,6) - α -D bonds naturally occurring starches typically contain relatively high levels of amylopectin such as corn starch (64-80% amylopectin), waxy corn (93-100% amylopectin), rice (83-84% amylopectin), potato (about 78% amylopectin), and wheat (73-83% amylopectin). although all starches are potentially useful herein, the most commonly used are high amylopectin native starches derived from agricultural sources, which provide the advantages of being plentiful, readily supplyable, and inexpensive.

As used herein, "starch" includes any naturally occurring unmodified starch, modified starch, synthetic starch, and mixtures thereof, as well as mixtures of amylose or amylopectin moieties; the starch may be modified by physical, chemical, or biological means, or a combination thereof. The choice of unmodified or modified starch may depend on the desired end product. In one embodiment, useful starches or starch mixtures have an amylopectin content of from about 20% to about 100%, more typically from about 40% to about 90%, even more typically from about 60% to about 85%, by weight of the starch or mixture thereof.

Suitable naturally occurring starches can include, but are not limited to, corn starch, potato starch, sweet potato starch, wheat starch, sago palm starch, tapioca starch, rice starch, soybean starch, arrowroot starch, amylopectin, fern root starch, lotus root starch, waxy corn starch, and high amylose corn starch. Naturally occurring starches, especially corn starch and wheat starch, are preferred starch polymers because of their economy and availability.

The polyvinyl alcohol herein may be grafted with other monomers to alter its properties. A number of monomers have been successfully grafted onto polyvinyl alcohol. Non-limiting examples of such monomers include vinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethyl methacrylate, acrylonitrile, 1, 3-butadiene, methyl methacrylate, methacrylic acid, maleic acid, itaconic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, sodium allyl phenyl ether sulfonate, sodium methallyl phenyl ether sulfonate, 2-acrylamide-methylpropanesulfonic Acid (AMP), vinylidene chloride, vinyl amine, and various acrylates.

In one example, the water-soluble hydroxyl polymer is selected from: polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and mixtures thereof. Non-limiting examples of suitable polyvinyl alcohols include those available under the trademark Sekisui specialty Chemicals America, LLC (Dallas, TX)Those commercially available. Non-limiting examples of suitable hydroxypropyl methylcelluloses include those available under the trade name Dow Chemical Company (Midland, Mich.)Those commercially available, including combinations with the polyvinyl alcohols mentioned above.

b.Water-soluble thermoplastic polymers

Non-limiting examples of suitable water-soluble thermoplastic polymers include thermoplastic starch and/or starch derivatives, polylactic acid, polyhydroxyalkanoates, polycaprolactones, polyesteramides and certain polyesters, and mixtures thereof.

The water soluble thermoplastic polymer may be hydrophilic or hydrophobic. The water-soluble thermoplastic polymer may be surface treated and/or internally treated to alter the inherent hydrophilic or hydrophobic character of the thermoplastic polymer.

The water soluble thermoplastic polymer may comprise a biodegradable polymer.

Any suitable weight average molecular weight thermoplastic polymer may be used. For example, the weight average molecular weight of the thermoplastic polymer may be greater than about 10,000g/mol, and/or greater than about 40,000g/mol, and/or greater than about 50,000g/mol, and/or less than about 500,000g/mol, and/or less than about 400,000g/mol, and/or less than about 200,000 g/mol.

ii.Non-polar solvent soluble material

Non-limiting examples of non-polar solvent soluble materials include non-polar solvent soluble polymers. Non-limiting examples of suitable non-polar solvent soluble materials include cellulose, chitin derivatives, polyolefins, polyesters, copolymers thereof, and mixtures thereof. Non-limiting examples of polyolefins include polypropylene, polyethylene, and mixtures thereof. Non-limiting examples of polyesters include polyethylene terephthalate.

The non-polar solvent soluble material may comprise non-biodegradable polymers such as polypropylene, polyethylene and certain polyesters.

C.Active agent

Active agents are a class of additives designed and intended to provide a benefit to something other than the filament itself, for example, to the environment outside the filament. The active agent can be any suitable additive that produces the desired effect under the conditions of intended use of the filament. For example, the active agent may be selected from: personal cleansing and/or conditioning agents, for example hair care agents such as shampoos and/or hair colorants, hair conditioning agents, skin care agents, sunscreens, and skin conditioning agents; laundry care and/or conditioning agents such as fabric care agents, fabric conditioners, fabric softeners, fabric anti-wrinkle agents, fabric care antistatic agents, fabric care detergents, dispersants, suds suppressors, suds boosters, defoamers, and fabric fresheners; liquid and/or powder dishwashing agents (for hand dishwashing and/or automatic dishwasher use), hard surface conditioning agents, and/or conditioning agents and/or polishing agents; other cleaning and/or conditioning agents such as antimicrobial agents, perfumes, bleaching agents (e.g., oxidative bleaches, hydrogen peroxide, percarbonate bleaches, perborate bleaches, chlorine bleaches), bleach activators, chelants, builders, emulsions, brighteners, air care agents, carpet care agents, dye transfer inhibitors, water softeners, water hardeners, pH adjusters, enzymes, flocculants, effervescing agents, preservatives, cosmetics, make-up removers, foaming agents, deposition aids, aggregate formers, clays, thickeners, latexes, silicas, dessicants, odor control agents, antiperspirants, cooling agents, warming agents, absorbent gels, anti-inflammatory agents, dyes, pigments, acids, and bases; a liquid treatment active; an agricultural active agent; an industrial active agent; ingestible actives such as therapeutic agents, tooth whiteners, tooth care agents, mouth washes, periodontal gum care agents, edible agents, dietary supplements, vitamins, minerals; water treatment agents such as water clarifiers and/or water disinfectants, and mixtures thereof.

Non-limiting examples of suitable Cosmetic agents, skin care agents, skin conditioning agents, hair care agents, and hair conditioning agents are described in CTFA Cosmetic Ingredient Handbook, second edition, The Cosmetic, Toiletries, and fragrance Association, inc.1988, 1992.

One or more classes of chemicals may be used for one or more of the active agents listed above. For example, surfactants can be used for any number of the above-mentioned active agents. Likewise, bleaching agents can be used for fabric care, hard surface cleaning, dishwashing and even tooth whitening. Thus, one of ordinary skill in the art will appreciate that the active agent will be selected based on the intended use of the filaments and/or nonwoven fabric made therefrom.

For example, if the filaments and/or nonwoven fabric made therefrom are to be used for hair care and/or conditioning, one or more suitable surfactants, such as lathering surfactants, can be selected to provide the desired benefit to the consumer when exposed to the intended use conditions of the filaments and/or nonwoven fabric incorporating the filaments.

In one example, if the filaments and/or nonwoven fabrics made therefrom are designed or intended for use in laundry in a laundering operation, one or more suitable surfactants, and/or enzymes, and/or builders, and/or perfumes, and/or suds suppressors, and/or bleaches may be selected to provide the desired benefit to the consumer upon exposure to the filaments and/or the conditions of intended use of the nonwoven fabric incorporating the filaments. In another example, if the filaments and/or nonwoven fabrics made therefrom are designed for use in laundry in a laundry operation and/or dish cleaning in a dish washing operation, the filaments may comprise a laundry detergent composition or a dish detergent composition.

In one example, the active agent comprises a non-fragrance active agent. In another example, the active agent comprises a surfactant-free active agent. In another example, the active agent includes an active agent that is not an ingestible active agent, in other words, is not an ingestible active agent.

i.Surface active agent

Non-limiting examples of suitable surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. The filaments may also include a co-surfactant. For filaments designed for use as laundry and/or dishwashing detergents, the total level of surfactant will be sufficient to provide cleaning, including stain cleaning and/or odor removal, and will generally range from about 0.5% to about 95%. Furthermore, surfactant systems comprising two or more surfactants are designed for use in filaments of laundry and/or dishwashing detergents, which may include all anionic surfactant systems, mixed surfactant systems comprising anionic-nonionic surfactant mixtures, or nonionic-cationic surfactant mixtures or low-foaming nonionic surfactants.

The surfactants herein may be linear or branched. In one example, suitable linear surfactants include those derived from agrochemical oils such as coconut oil, palm kernel oil, soybean oil, or other vegetable oils.

a.Anionic surfactants

Non-limiting examples of suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, branched alkyl alkoxylates, branched alkyl alkoxylate sulfates, mid-chain branched alkyl aryl sulfonates, sulfated monoglycerides, sulfonated olefins, alkyl aryl sulfonates, primary or secondary alkane sulfonates, alkyl succinate sulfonates, acyl taurates, acyl isethionates, alkyl glyceryl ether sulfonates, sulfonated methyl esters, sulfonated fatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl sulfoacetates, acylated peptides, alkyl ether carboxylates, acyl lactylates, anionic fluorosurfactants, sodium lauroyl glutamate, and combinations thereof.

Suitable alkyl sulfates and alkyl ether sulfates for use herein include those having the corresponding formula ROSO₃M and RO (C)₂H₄O)_xSO₃M, wherein R is an alkyl or alkenyl group having from about 8 to about 24 carbon atoms, x is from 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium, and triethanolamine. Other suitable anionic surfactants are described in McCutcheon "detergents and Emulsifiers", North American edition (1986), Allured Publishing Corp. and McCutcheon's "Functional Materials", North American edition (1992), Allured Publishing Corp.

In one example, anionic surfactants useful in the filaments can include C₉-C₁₅Alkyl benzene sulfonate (LAS), C₈-C₂₀Alkyl ether sulfates, e.g. alkyl poly (ethoxy) sulfates, C₈-C₂₀Alkyl sulfates, and mixtures thereof. Other anionic surfactants include Methyl Ester Sulfonates (MES), secondary alkane sulfonates, Methyl Ester Ethoxylates (MEE), sulfonated anhydrides, and mixtures thereof.

In another example, the anionic surfactant is selected from: c₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary branched random C₁₀-C₂₀Alkyl sulfates ("AS"), C₁₀-C₁₈A secondary (2,3) alkyl sulfate of the formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃Wherein x and (y +1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, an unsaturated sulfate such as oleyl sulfate, C₁₀-C₁₈α sulfonated fatty acid ester, C₁₀-C₁₈Sulfated alkyl polyglycoside, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS'), wherein x is 1-30, and C₁₀-C₁₈An alkyl alkoxy formate, which is a mixture of alkyl alkoxy formates,for example mid-chain branched alkyl sulfates containing from 1 to 5 ethoxy units, as described in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443, mid-chain branched alkyl alkoxy sulfates as described in U.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303, modified alkyl benzene sulfonates (MLAS) as described in WO99/05243, WO 99/05242 and WO 99/05244, Methyl Ester Sulfonates (MES), and α -olefin sulfonates (AOS).

Other suitable anionic surfactants that may be used are alkyl ester sulfonate surfactants, including C₈-C₂₀Sulfonated linear esters of carboxylic acids (i.e., fatty acids). Other suitable anionic surfactants that may be used include soap salts, C₈-C₂₂Primary and secondary alkanesulfonates, C₈-C₂₄Olefin sulfonate, sulfonated polycarboxylic acid, C₈-C₂₄Alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glyceryl sulfonates, fatty acyl glyceryl sulfonates, fatty oleoyl glyceryl sulfates, alkylphenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinic acid monoesters (e.g. saturated and unsaturated C)₁₂-C₁₈Monoesters) and sulfosuccinic acid diesters (e.g., saturated and unsaturated C)₆-C₁₂Diesters), sulfates of alkyl polysaccharides such as alkyl polyglucoside sulfates, and alkyl polyethoxy carboxylates such as those having the formula RO (CH)₂CH₂O)_k-CH₂COO-M + wherein R is C₈-C₂₂Alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation.

Other exemplary anionic surfactant is C₁₀-C₁₆Alkali metal salts of linear alkyl benzene sulphonic acids, preferably C₁₁-C₁₄Alkali metal salts of linear alkyl benzene sulphonic acids. In one example, the alkyl group is linear. Such linear alkyl benzene sulphonates are known as "LAS". Such surfactants and their preparation are described, for example, in U.S. Pat. nos. 2,220,099 and 2,477,383. In another example, straight chain alkyl groupsThe benzene sulfonate comprises sodium and/or potassium linear alkyl benzene sulfonate wherein the average number of carbon atoms on the alkyl group is from about 11 to 14. C₁₁-C₁₄Sodium linear alkyl benzene sulphonates such as C₁₂Sodium linear alkyl benzene sulphonate is a specific example of such a surfactant.

Another exemplary type of anionic surfactant includes linear or branched ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylated sulfates, are those corresponding to the formula: r' -O- (C)₂H₄O)_n-SO₃M, wherein R' is C₈-C₂₀An alkyl group, n is about 1 to 20, and M is a salt-forming cation. In a particular embodiment, R' is C₁₀-C₁₈Alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is C₁₂-C₁₆N is about 1 to 6 and M is sodium. The alkyl ether sulfates are generally used in the form of mixtures comprising different R' chain lengths and different degrees of ethoxylation. Typically, such mixtures will also inevitably contain certain non-ethoxylated alkyl sulfate materials, i.e., surfactants in which n is 0in the above ethoxylated alkyl sulfate formula. The non-ethoxylated alkyl sulfate may also be added separately to the composition and used as or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated (e.g. non-ethoxylated) alkyl ether sulfate surfactants are those which are built up by higher C₈-C₂₀Those resulting from the sulfation of fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: r' OSO₃ ^-M⁺Wherein R' is typically C₈-C₂₀An alkyl group, which may be linear or branched, and M is a water-solubilizing cation. In a specific embodiment, R' is C₁₀-C₁₅An alkyl group, and M is an alkali metal, more specifically, R' is C₁₂-C₁₄Alkyl, and M is sodium. Specific non-limiting examples of anionic surfactants useful herein include: a) c₁₁-C₁₈Alkyl radicalBenzenesulfonate (LAS); b) c₁₀-C₂₀Primary, branched and random Alkyl Sulfates (AS); c) c having the formula₁₀-C₁₈Secondary (2,3) -alkyl sulfates:

wherein M is hydrogen or a cation that provides electroneutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can be hydrogen atoms or cations, depending on the form isolated by the skilled artisan or the relative pH of the system in which the compound is used, wherein non-limiting examples of suitable cations include sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7 and/or at least about 9, and y is an integer of at least 8 and/or at least 9; d) c₁₀-C₁₈Alkyl alkoxy sulfates (AE)_zS), wherein z is, for example, from 1 to 30; e) c preferably containing 1 to 5 ethoxy units₁₀-C₁₈Alkyl alkoxy carboxylates f) mid-chain branched alkyl sulfates as discussed in U.S. Pat. Nos. 6,020,303 and 6,060,443, g) mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. Nos. 6,008,181 and 6,020,303, h) modified alkyl benzene sulfonates (MLAS) as discussed in WO99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO99/05241, WO 99/07656, WO 00/23549 and WO 00/23548, i) Methyl Ester Sulfonates (MES), and j) α -olefin sulfonates (AOS).

b.Cationic surfactant

Non-limiting examples of suitable cationic surfactants can include, but are not limited to, those having the formula (I):

wherein R is¹、R²、R³And, andR⁴each independently selected from (a) an aliphatic group having from 1 to about 26 carbon atoms, or (b) an aryl, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion, such as a group selected from halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate. In one example, the alkyl sulfate is methyl sulfate and/or ethyl sulfate.

Suitable quaternary ammonium cationic surfactants having general formula (I) can include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride (BTAC), stearyltrimethylammonium chloride, cetylpyridinium chloride, octadecyltrimethylammonium chloride, cetyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, distearyldimethylammonium chloride, tallowyltrimethylammonium chloride, cocoyltrimethylammonium chloride, 2-ethylhexylstearyldimethylammonium chloride, dipalmitoylethyldimethylammonium chloride, PEG-2 oleylammonium chloride, and salts of these, wherein the chloride ion is replaced with a halogen (e.g., bromide), acetate, citrate, sulfate, lactate, glycolate, phosphate, nitrate, sulfate, or alkylsulfate substitutions.

Non-limiting examples of suitable cationic surfactants are available under the trademark "WAXPurchased from Akzo NobelSurfactants (Chicago, IL).

In one example, suitable cationic surfactants include quaternary ammonium (ionic) surfactants, such as surfactants having up to 26 carbon atoms, including: alkoxylated Quaternary Ammonium (AQA) surfactants as described in US6,136,769; dimethyl hydroxyethyl quaternary ammonium as described in 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants, as described in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005 and WO 98/35006; cationic ester surfactants as described in U.S. Pat. nos. 4,228,042, 4,239,6604,260,529 and 6,022,844; and amino surfactants such as amidopropyl dimethylamine (APA) discussed in US6,221,825 and WO 00/47708.

Other suitable cationic surfactants include salts of primary, secondary and tertiary fatty amines. In one embodiment, the alkyl groups of such amines have from about 12 to about 22 carbon atoms and may be substituted or unsubstituted. These amines are typically used in combination with an acid to provide the cationic species.

The cationic surfactant may comprise a cationic ester surfactant having the formula:

wherein R is₁Is C₅-C₃₁Straight-chain or branched alkyl, alkenyl or alkylaryl chains or M^-.N⁺(R₆R₇R₈)(CH₂)_s(ii) a X and Y are independently selected from: COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH, and NHCOO, wherein at least one of X or Y is a COO, OCO, OCOO, OCONH, or NHCOO group; r₂、R₃、R₄、R₆、R₇And R₈Independently selected from: alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R is₅Independently is hydrogen or C₁-C₃An alkyl group; wherein the values of m, n, s and t independently range from 0 to 8, the value of b ranges from 0 to 20, and the values of a, u and v independently are 0 or 1, provided that at least one of u or v must be 1; and wherein M is a counter anion. In one example, R₂、R₃And R₄Independently selected from CH₃and-CH₂CH₂And (5) OH. In another example, MSelected from: halide, methyl sulfate, nitrate, chloride, bromide, or iodide.

Cationic surfactants may be selected for personal cleansing applications. In one example, the total level of such cationic surfactants that may be included in the filaments and/or fibers is from about 0.1% to about 10%, and/or from about 0.5% to about 8%, and/or from about 1% to about 5%, and/or from about 1.4% to about 4% by weight, in view of the balance of easy rinse feel, rheology, and wet conditioning benefits. A variety of cationic surfactants, including mono-and di-alkyl chain cationic surfactants, can be used in the composition. In one example, to provide the desired gel matrix and wet conditioning benefits, the cationic surfactant comprises a single alkyl chain cationic surfactant. To provide balanced wet conditioning benefits, the mono-alkyl cationic surfactants are those having one long alkyl chain with 12 to 22 carbon atoms, and/or 16 to 22 carbon atoms, and/or 18 to 22 carbon atoms. The other groups attached to the nitrogen are independently selected from alkyl groups having from 1 to about 4 carbon atoms, or alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl groups having up to about 4 carbon atoms. The above-mentioned monoalkyl cationic surfactants include, for example, monoalkyl quaternary ammonium salts and monoalkyl amines. Monoalkyl quats include, for example, those having a long chain of non-functionalized alkyl groups. Monoalkylamines include, for example, monoalkylamidoamines and salts thereof. Other cationic surfactants such as dialkyl chain cationic surfactants may also be used alone or in combination with monoalkyl chain cationic surfactants. The above-mentioned dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride and dicetyl dimethyl ammonium chloride.

In one example, the cationic ester surfactant is hydrolyzable under laundry washing conditions.

c.Nonionic surfactant

Non-limiting examples of suitable nonionic surfactants include alkoxylated Alcohols (AE) and alkyl phenols, Polyhydroxy Fatty Acid Amides (PFAA), Alkyl Polyglycosides (APG), C₁₀-C₁₈Glycerol ethers, and the like.

In one example, non-limiting examples of useful nonionic surfactants include: c₁₂-C₁₈Alkyl ethoxylates, e.g. from ShellA nonionic surfactant; c₆-C₁₂An alkylphenol alkoxylate wherein the alkoxylate unit is a mixture of ethyleneoxy and propyleneoxy units; c₁₂-C₁₈Alcohol and C₆-C₁₂Condensates of alkylphenols with ethylene oxide/propylene oxide block alkylpolyamine ethoxylates, e.g. from BASFC₁₄-C₂₂Mid-chain branched alcohols, BA, as discussed in US6,150,322; c₁₄-C₂₂Mid-chain branched alkyl alkoxylate BAE_xWherein x is 1-30, as discussed in US6,153,577, US6,020,303 and US6,093,856; alkyl polysaccharides such as described in US 4,565,647 to lleado published on 26.1.1986; in particular, alkyl polyglycosides as described in US 4,483,780 and US 4,483,779; polyhydroxy detergent acid amides, as discussed in US 5,332,528; and ether-terminated poly (alkoxylated) alcohol surfactants as described in US6,482,994 and WO 01/42408.

Examples of suitable commercially available nonionic surfactants include: all available from Dow chemical company15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 mol of ethylene oxide) and24-L-6 NMW(C₁₂-C₁₄condensation products of primary alcohols with 6 moles of ethylene oxide with narrow molecular weight distribution); sold by Shell chemical Company45-9(C₁₄-C₁₅Condensation products of straight-chain alcohols with 9 mol of ethylene oxide)23-3(C₁₂-C₁₃Condensation products of straight-chain alcohols with 3 mol of ethylene oxide) and,45-7(C₁₄-C₁₅Condensation products of linear alcohols with 7 mol of ethylene oxide) and45-5(C₁₄-C₁₅condensation products of linear alcohols with 5 moles of ethylene oxide); sold by The Procter&Of Gamble CompanyEOB (condensation product of a C13-C15 alcohol with 9 moles of ethylene oxide); and Genapol LA O3O or O5O (C) available from Hoechst₁₂-C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide). The nonionic surfactant can exhibit an HLB in the range of from about 8 to about 17 and/or from about 8 to about 14. Condensation products with propylene oxide and/or butylene oxide may also be used.

Non-limiting examples of useful semi-polar nonionic surfactants include: a water-soluble amine oxide comprising one alkyl moiety having from about 10 to about 18 carbon atoms, and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms; a water-soluble phosphine oxide comprising one alkyl moiety having from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of: alkyl and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and a water-soluble sulfoxide comprising an alkyl moiety having from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of: alkyl moieties and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681,704 and US 4,133,779.

Another class of nonionic surfactants that can be used include polyhydroxy fatty acid amide surfactants having the formula:

wherein R is¹Is hydrogen, or C_1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R₂Is C_5-31Hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain of at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof. In one example, R¹Is methyl, R₂Is C_11-15Alkyl straight chain or C_15-17Straight chain alkyl or alkenyl, such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction. Typical examples include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamine.

Alkyl polysaccharide surfactants may also be used as nonionic surfactants.

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols are also suitable for use as nonionic surfactants. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, which forms a straight or branched chain configuration with alkylene oxides. Commercially available nonionic surfactants of this type includeCO-630, available from GAF Corporation; andx-45, X-114, X-100, and X-102, all available from the Dow Chemical Company.

For automatic dishwashing applications, low foaming nonionic surfactants may be used. Suitable low foaming nonionic surfactants are disclosed in US7,271,138, column 7, line 10 to column 7, line 60.

Examples of other suitable nonionic surfactants are commercially availableSurfactants, available from BASF; commercially availableCompounds, available from BASF; and commercially availableSurfactant, available from BASF.

d.Zwitterionic surfactants

Non-limiting examples of zwitterionic or amphoteric surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium, quaternary phosphoniumOr a derivative of a tertiary sulfonium compound. For examples of zwitterionic surfactants, see U.S. Pat. No. 3,929,678 at column 19, line 38 to column 22, line 48; betaines, including alkyldimethyl betaine and coco dimethyl amidopropyl betaine, C₈-C₁₈(e.g. C)₁₂-C₁₈) Amine oxides and sulpho and hydroxy betaines, e.g. N-alkyl-N, N-dimethylamino-1-propanesulphonate, wherein the alkyl group may be C₈-C₁₈And in certain embodiments is C₁₀-C₁₄。

e.Amphoteric surfactant

Non-limiting examples of amphoteric surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain, and mixtures thereof. One aliphatic substituent may comprise at least about 8 carbon atoms, for example from about 8 to about 18 carbon atoms, and at least one comprises a water-solubilizing anionic group, such as carboxy, sulfonate, sulfate. Examples of suitable amphoteric surfactants are described in U.S. Pat. No. 3,929,678 at column 19, lines 18 through 35.

f.Cosurfactant

In addition to the surfactants described above, the filaments may also contain co-surfactants. For laundry and/or dishwashing detergents, they typically comprise a mixture of various types of surfactants to achieve broad cleaning performance over a wide range of soils and stains and under a wide range of use conditions. A wide variety of these co-surfactants are available for use in the filaments. Typical lists of anionic, nonionic, amphoteric and zwitterionic classes and these co-surfactant materials are given above and can also be found in U.S. patent publication 3,664,961. In other words, the surfactant system herein may also comprise one or more co-surfactants selected from nonionic, cationic, anionic, zwitterionic or mixtures thereof. The choice of co-surfactant may be dictated by the desired benefit. The surfactant system may comprise from 0% to about 10%, or from about 0.1% to about 5%, or from about 1% to about 4%, by weight of the composition, of other co-surfactants.

g.Amine neutralized anionic surfactants

The anionic surfactant and/or anionic co-surfactant may be present in the acid form, which may be neutralized to form a surfactant salt. In one example, the filaments may comprise a surfactant in the form of a salt. Typical reagents for neutralization include basic metal counterions such as hydroxides, for example sodium hydroxide or potassium hydroxide. Other agents for neutralizing the acid form of the anionic surfactant and anionic co-surfactant include ammonia, amines, or alkanolamines. In one example, the neutralizing agent includes an alkanolamine, such as an alkanolamine selected from the group consisting of: monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; such as 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. The amine neutralization may be partial or complete, for example, part of the anionic surfactant may be neutralized with sodium or potassium and part of the anionic surfactant may be neutralized with an amine or alkanolamine.

Perfume ii

One or more fragrances and/or fragrance raw materials such as accords and/or fragrances may be incorporated into one or more filaments. The perfume may comprise perfume ingredients selected from: aldehyde perfume ingredients, ketone perfume ingredients, and mixtures thereof.

The filaments may include one or more fragrances and/or fragrance ingredients. Numerous natural and synthetic chemical ingredients useful as perfumes and/or perfume ingredients include, but are not limited to, aldehydes, ketones, esters, and mixtures thereof. Also included are various natural extracts and essential oils, which include complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamine essential oil, sandalwood oil, pine oil, cedar, and the like. Refined flavours may comprise extremely complex mixtures of such ingredients. In one example, finished perfumes typically comprise from about 0.01% to about 2% by weight on a dry filament basis and/or on a dry web material basis.

Perfume delivery system iii

Certain perfume delivery systems, methods of making certain perfume delivery systems, and uses of such perfume delivery systems are disclosed in U.S. patent application publication 2007/0275866. Non-limiting examples of perfume delivery systems include the following:

polymer Assisted Delivery (PAD): the perfume delivery technology uses polymeric materials to deliver perfume materials. Some examples are the agglomeration of typical water soluble or partially water soluble materials into insoluble charged or neutral polymers, liquid crystals, hot melts, hydrogels, fragrance filled plastics, microcapsules, nano and micro latexes, polymeric film formers and polymeric absorbents, polymeric adsorbents, and the like. PAD includes, but is not limited to:

a.)matrix system: the fragrance is dissolved or dispersed in a polymer matrix or particle. The perfume, for example, can be added separately from the polymer, either 1) dispersed into the polymer prior to formulation into the product, or 2) during or after formulation of the product. While many other triggers are known that can control the release of perfume, diffusion of perfume from a polymer is a common trigger that allows or increases the rate of perfume release from a polymer matrix system that is deposited or applied to a desired surface (site). Absorption and/or adsorption onto or into polymer particles, membranes, solutions, etc. is an aspect of this technology. Nano-or micro-particles of organic material (e.g., emulsion) are examples. Suitable particles include a wide variety of materials including, but not limited to, polyacetals, polyacrylates, polyacrylics, polyacrylonitriles, polyamides, polyaryletherketones, polybutadienes, polybutylenes, polybutylene terephthalates, polychloroprenes, polyethylenes, polyethylene terephthalates, cyclohexylenedimethylene terephthalates, polycarbonates, polychloroprenes, polyhydroxyalkanoates, polyketones, polyesters, polyethylenes, polyetherimides, polyethersulfones, chlorinated polyethylenes, polyimides, polyisoprenes, polylactic acids, polymethylpentenes, polyphenylene oxides, polyphenylene sulfides, polyphthalamides, polypropylenes, polystyrenes, polysulfones, polyvinyl acetates, polyvinyl chlorides, and polymers based on acrylonitrile-butadiene, cellulose acetate, ethylene-vinyl acetates, ethylene-vinyl alcohols, styrene-butadiene, poly (trimethylene terephthalate), poly (tetramethylene terephthalate), poly (, Vinyl acetate-ethylene polymers or copolymers, and mixtures thereof.

"Standard" systems are those that are "preloaded" for the purpose of keeping the preloaded perfume associated with the polymer until the time or times of perfume release. Depending on the rate of perfume release, such polymers may also suppress the neat product odor and provide bloom and/or shelf life benefits. One challenge with such systems is to achieve a desirable balance between: 1) stability in the product (hold the perfume in the carrier until you want it) and 2) timely release (during use or from the dry site). Obtaining such stability is especially important during storage in the product and product aging. This challenge is particularly evident with aqueous-based, surfactant-containing products, such as heavy duty liquid laundry detergents. Many "standard" matrix systems that are effectively obtained become "balanced" systems when formulated into aqueous-based products. One can select a "balanced" system or a storage system that has acceptable in-product diffusion stability and available triggers for release (e.g., friction). An "equilibrium" system is one in which the perfume and polymer can be added separately to the product, and the equilibrium interaction between the perfume and polymer results in a benefit at one or more points of consumer contact (relative to free perfume without polymer assisted delivery technology). The polymer may also be pre-loaded with perfume; however, some or all of the perfume may diffuse during storage in the product to reach an equilibrium that includes having a desired Perfume Raw Material (PRM) associated with the polymer. The polymer then carries the perfume to the surface, and release is typically via perfume diffusion. The use of such equilibrium system polymers has the potential to reduce the neat product odor intensity of the neat product (typically more so in the case of pre-loaded standard systems). Deposition of such polymers serves to "flatten" the release characteristics and provide increased shelf life. As described above, such shelf life would be obtained by suppressing the initial intensity, and may enable the formulator to use a higher impact or low Odor Detection Threshold (ODT) or low Kovat's Index (KI) PRM to obtain FMOT benefits without the need for too strong or distorted initial intensity. It is important that perfume release occurs within the time frame of application to affect the desired consumer contact or contacts. Suitable microparticles and microemulsions and their methods of manufacture can be found in USPA 2005/0003980a 1. Matrix systems also include hot melt adhesives and flavor plastics. In addition, hydrophobically modified polysaccharides can be formulated into perfumed products to increase perfume deposition and/or improve perfume release. All such matrix systems including, for example, polysaccharides and nanolatexes, may be combined with other PDT, including other PAD systems such as PAD storage systems in the form of Perfume Microcapsules (PMC). Polymer Assisted Delivery (PAD) matrix systems may include those described in the following references: U.S. patent application publication 2004/0110648 a 1; 2004/0092414A 1; 2004/0091445A 1 and 2004/0087476A 1; and U.S. patent 6,531,444; 6,024,943; 6,042,792; 6,051,540, respectively; 4,540,721, and 4,973,422.

Silicones are also examples of polymers that can be used as PDT and can provide a fragrance benefit in a manner similar to polymer assisted delivery "matrix systems". Such PDT is known as Silicone Assisted Delivery (SAD). One can preload silicones with fragrance or use them as an equilibrium system as described for PAD. Suitable siloxanes and methods for their preparation are presented in WO 2005/102261; U.S. patent application publication 2005/0124530a 1; U.S. patent application publication 2005/0143282a 1; and in WO 2003/015736. Functionalized silicones may also be used, as described in U.S. patent application publication 2006/003913A 1. Examples of silicones include polydimethylsiloxane and polyalkyldimethylsiloxanes. Other examples include those with amine functionality, which can be used to provide benefits associated with Amine Assisted Delivery (AAD) and/or Polymer Assisted Delivery (PAD) and/or Amine Reaction Products (ARP). Other such examples can be found in us patent 4,911,852; and U.S. patent application 2004/0058845 a 1; 2004/0092425A 1 and 2005/0003980A 1.

b.)Storage system: storage systems are also known as the core/shell type technology, or where the fragrance is one surrounded by a perfume release controlling membrane, which can serve as a protective shell. The material inside the microcapsules is called the core, internal phase or filler, andthe wall is sometimes referred to as a shell, coating or film. Microparticles or pressure sensitive capsules or microcapsules are examples of such techniques. The microcapsules of the present invention are formed by a variety of procedures including, but not limited to, coating, extrusion, spray drying, interfacial, in situ, and templated polymerization. Possible shell materials vary greatly in their stability to water. Among the most stable are Polyhydroxymethylurea (PMU) based materials that can retain certain PRMs in aqueous solution (or product) for even longer periods of time. Such systems include, but are not limited to, urea formaldehyde and/or melamine formaldehyde. Stable shell materials include polyacrylate-based materials obtained as the reaction product of an oil-soluble or dispersible amine with a multifunctional acrylate or methacrylate monomer or oligomer, an oil-soluble acid, and an initiator in the presence of an anionic emulsifier comprising a water-soluble or water-dispersible acrylic alkyl acid copolymer, a base or base salt. The gum-based microcapsules may be prepared so that they dissolve rapidly or slowly in water, depending on, for example, the degree of crosslinking. Many other capsule wall materials are available and variations in the degree of perfume diffusion stability are observed. Without being bound by theory, for example, the rate of perfume release from the capsules once deposited onto a surface is generally in reverse order of perfume diffusion stability in the product. Likewise, for example, urea formaldehyde and melamine formaldehyde microcapsules typically require a release mechanism other than or in addition to diffusion release, such as mechanical forces (e.g., friction, pressure, shear stress) that serve to break the capsules and increase the rate of perfume (fragrance) release. Other triggers include melting, dissolution, hydrolysis or other chemical reactions, electromagnetic radiation, and the like. The use of pre-loaded microcapsules requires appropriate ratios of stability in the product and release in the application and/or on the surface (at the site), as well as appropriate selection of PRMs. Microcapsules based on urea formaldehyde and/or melamine formaldehyde are relatively stable, especially in near neutral aqueous based solutions. These materials may require a frictional trigger, which is not suitable for all product applications. Other microcapsule materials (e.g., gums) can be unstable in aqueous-based products and can even provide reduced benefits (relative to free perfume controls) when aged in the product. The scraping and fragrance generating technology comprisesAnother example of a PAD. Perfume Microcapsules (PMCs) may include those described in the following references: U.S. patent application publication: 2003/0125222A 1; 2003/215417A 1; 2003/216488A 1; 2003/158344A 1; 2003/165692A 1; 2004/071742A 1; 2004/071746A 1; 2004/072719A 1; 2004/072720A 1; 2006/0039934A 1; 2003/203829A 1; 2003/195133A 1; 2004/087477A 1; 2004/0106536A 1; and U.S. patent 6,645,479B 1; 6,200,949B 1; 4,882,220, respectively; 4,917,920, respectively; 4,514,461, respectively; 6,106,875 and 4,234,627, 3,594,328 and US RE32713, PCT patent application: WO 2009/134234 a1, WO 2006/127454 a2, WO 2010/079466 a2, WO 2010/079467 a2, WO2010/079468 a2, WO 2010/084480 a 2.

Molecular Assisted Delivery (MAD): non-polymeric materials or molecules may also be used to improve the delivery of perfume. Without being bound by theory, the perfume may interact non-covalently with the organic material, resulting in altered deposition and/or release. Non-limiting examples of such organic materials include, but are not limited to: hydrophobic materials such as engine oils, waxes, mineral oils, petrolatum, fatty acids or esters, sugars, surfactants, liposomes and even other perfume raw materials (perfume oils), as well as natural oils, including body and/or other soils. Perfume fixatives are another example. In one aspect, the non-polymeric material or molecule has a CLogP of greater than about 2. Molecular Assisted Delivery (MAD) may also include those described in U.S. patents 7,119,060 and 5,506,201.

Fiber Assisted Delivery (FAD): the choice or use of the situs itself can be used to improve perfume delivery. Indeed, the situs itself may be a perfume delivery technology. For example, different fabric types, such as cotton or polyester, will have different properties with respect to their ability to attract and/or retain and/or release perfume. The amount of perfume deposited onto or within the fibers can be varied by the choice of fiber, and also by the history or treatment of the fiber, as well as by any fiber coating or treatment. The fibers may be woven and non-woven, as well as natural or synthetic. Natural fibers include those made from plant, animal and geological processes, including but not limited to celluloseMaterials such as cotton, linen, hemp, jute, flax, ramie and pineapple, and fibers used to make paper and cloth. Fiber-assisted delivery may include the use of wood fibers, such as thermomechanical wood pulp and bleached or unbleached kraft or sulfite pulp. Animal fibers are composed of a large number of specific proteins, such as silk, tendons, gut and hair (including wool). Synthetic chemistry based polymer fibers include, but are not limited to, polyamide nylon, PET or PBT polyester, Phenol Formaldehyde (PF), polyvinyl alcohol fibers (PVOH), polyvinyl chloride fibers (PVC), polyolefins (PP and PE), and acrylic polymers. All such fibers may be pre-loaded with perfume and then added to a product, which may or may not include free perfume and/or one or more perfume delivery technologies. In one aspect, the fibers can be added to the product prior to loading with the perfume, and then loaded with the perfume by adding the perfume, which can diffuse into the fibers, into the product. Without being bound by theory, the flavorant may be absorbed onto or into the fiber, for example, during storage of the product, and then released at one or more precise or consumer contact points.

Amine Assisted Delivery (AAD): amine assisted delivery technology approaches utilize materials containing amine groups to increase perfume deposition or improve perfume release during product use. There is no need in this process to pre-complex or pre-react the perfume raw material and amine prior to addition to the product. In one aspect, amine-containing AAD materials suitable for use herein can be non-aromatic; for example, polyalkyleneimines, such as Polyethyleneimine (PEI) or polyvinylamine (PVAm) or aromatic, for example anthranilates. Such materials may also be polymeric or non-polymeric. In one aspect, such materials comprise at least one primary amine. Without being bound by theory, for polymeric amines, this technique would allow for increased shelf-life and controlled release of the same low ODT perfume fragrance (e.g., aldehydes, ketones, ketenes) relative to amine functionality, as well as delivery of other PRMs, by polymer assisted delivery. Without this technique, the volatile top notes would be lost too quickly, leaving a higher ratio of middle and bottom notes to top notes. The use of polymeric amines allows for higher levels of top notesAnd other PRMs are used to achieve a fresh shelf life without causing the neat product to smell more strongly than desired, or allowing the top notes and other PRMs to be used more efficiently. In one aspect, the AAD system is effective to deliver the PRM at a pH greater than about neutral. Without being bound by theory, the conditions under which more of the amine of the AAD system is deprotonated will result in increased affinity for the deprotonated amine of PRMs, such as aldehydes and ketones, including unsaturated ketones and enones, such as damascone. In another aspect, the polymeric amine is effective to deliver the PRM at a pH of less than about neutral. Without being bound by theory, the conditions in which more of the amine of the AAD system is protonated result in reduced affinity for PRMs, such as aldehyde and ketone protonated amines, and strong affinity for a wide range of PRM polymer backbones. In such an aspect, polymer-assisted delivery can deliver more perfuming benefits; such systems are a subspecies of AAD and may be referred to as amine-polymer assisted delivery or APAD. In some cases, such APAD systems may also be considered Polymer Assisted Delivery (PAD) when the APAD is used in compositions having a pH of less than seven. In yet another aspect, the AAD and PAD systems interact with other materials, such as anionic surfactants or polymers, to form coacervates and/or coacervate-like systems. In another aspect, materials containing heteroatoms other than nitrogen, such as sulfur, phosphorus, or selenium, may be used as an alternative amine compound. In yet another aspect, the aforementioned alternative compounds can be used in combination with an amine compound. In yet another aspect, a single molecule can comprise an amine moiety and one or more alternative heteroatom moieties, for example, thiols, phosphines, and selenols. Suitable AAD systems and methods for making the systems can be found in U.S. patent application publication 2005/0003980a 1; 2003/0199422A 1; 2003/0036489A 1; 2004/0220074a1 and us6,103,678.

Cyclodextrin delivery system (CD): the technical approach uses cyclic oligosaccharides or cyclodextrins to improve perfume delivery. Perfume and Cyclodextrin (CD) complexes are typically formed. Such complexes may be preformed, formed in situ, or formed on or within the site. Without being bound by theory, the loss of water will serve to shift the equilibrium towards CD-perfume complexesThe compound is directionally transferred, especially if other adjunct ingredients (such as surfactants) are not present in high concentrations and compete with the perfume for the cyclodextrin cavity. A bloom benefit may be obtained if exposure to water or increasing the water content occurs at a later point in time. In addition, cyclodextrins allow perfume formulators to increase flexibility in selecting PRMs. The cyclodextrin can be pre-loaded with perfume or added separately from perfume to achieve the desired perfume stability, deposition or release benefit. Suitable CDs and methods of making the CDs can be found in U.S. patent application publications 2005/0003980a1 and 2006/0263313 a1 and U.S. patent nos. 5,552,378; 3,812,011; 4,317,881; 4,418,144 and 4,378,923.

Starch capsule sealing blend (SEA): the use of Starch Encapsulated Accord (SEA) technology allows one to improve the properties of the perfume, for example, by converting a liquid perfume into a solid by adding ingredients such as starch. The benefits include increased perfume retention during product storage, especially under non-aqueous conditions. Upon exposure to water, perfume bloom may be triggered. Benefits at precisely other times may also be obtained because the starch allows the product formulator to select a PRM or PRM concentration that would not normally be used in the absence of SEA. Another example of technology involves the use of other organic and inorganic materials, such as silica, to convert the fragrance from a liquid to a solid. Suitable SEA and methods for preparing the SEA can be found in U.S. patent application publication 2005/0003980a1 and U.S. patent 6,458,754B 1.

Inorganic carrier delivery system (ZIC): this technology involves the use of porous zeolites or other inorganic materials to deliver perfume. The perfume-loaded zeolite may be used with or without adjunct ingredients, for example to coat the perfume-loaded zeolite (PLZ) to modify its perfume release properties during product storage or during use or from the dry site. Suitable zeolites and inorganic supports and methods for preparing the supports can be found in U.S. patent application publication 2005/0003980a1 and U.S. patent 5,858,959; 6,245,732B 1; 6,048,830, and 4,539,135. Oxidation of hydrogen dioxideSilicon is another form of ZIC. Another example of a suitable inorganic carrier includes an inorganic tubule, wherein the fragrance or other active is contained within the lumen of the nano-or micro-tubule. In one aspect, the perfume-loaded inorganic tubule (or perfume-loaded tubule or PLT) is a mineral nano-or micro-tubule, such as halloysite or mixtures of halloysite with other inorganic materials, including other clays. The PLT technology may also include additional ingredients inside and/or outside the tubule for improving diffusion stability in the product, for the purpose of deposition at a desired site, or for controlling the release of a loaded perfume. Monomeric and/or polymeric materials, including starch encapsulation, may be used to coat, plug, cap or otherwise encapsulate the PLT. Suitable PLT systems and methods for making the systems can be found in U.S. patent 5,651,976.

Fore spice (PP)The pro-perfumes include monomeric (non-polymeric) or polymeric ones, and may be preformed or may be formed in situ under equilibrium conditions, such as those that may be present during storage in a product or on a wet or dry locusAnother aspect includes compounds comprising one or more β -oxo or β -thiocarbonyl moieties capable of releasing PRMs, e.g., α - β -unsaturated ketones, aldehydes or carboxylic acid esters.Although other triggers may include enzymes, heat, light, pH change, autoxidation, shift in equilibrium, change in concentration or ion concentration, among others. For aqueous-based products, light-triggered pro-fragrances are particularly suitable. Such photo-pro-fragrances (PPPs) include, but are not limited to, those that release a coumarin derivative and a fragrance and/or pro-fragrance upon triggering. The released pro-perfume may release one or more PRMs by any of the above triggers. In one aspect, the photo-pro-fragrance releases a nitrogen-based pro-fragrance when triggered by exposure to light and/or moisture. In another aspect, the nitrogen-based pro-perfume released by the photo-pro-perfume releases one or more PRMs selected from, for example, aldehydes, ketones (including enones), and alcohols. In yet another aspect, the PPP releases a dihydroxycoumarin derivative. The light-triggered pro-fragrance can also be, in one aspect, an ester that releases a coumarin derivative and a fragrance alcohol, the pro-fragrance being a benzoin bis-methyl ether derivative described in U.S. patent application publication 2006/0020459A 1. In another aspect, the pro-fragrance is a 3 ', 5' -benzoin dimethyl ether (DMB) derivative that releases an alcohol upon exposure to electromagnetic radiation. In yet another aspect, the pro-perfume releases one or more low ODT PRMs, including tertiary alcohols, such as linalool, tetrahydrolinalool, or dihydromyrcenol. Suitable pro-perfumes and methods of making the pro-perfumes can be found in U.S. Pat. nos. 7,018,978B 2; 6,987,084B 2; 6,956,013B 2; 6,861,402B 1; 6,544,945B 1; 6,093,691, respectively; 6,277,796B 1; 6,165,953, respectively; 6,316,397B 1; 6,437,150B 1; 6,479,682B 1; 6,096,918, respectively; 6,218,355B 1; 6,133,228, respectively; 6,147,037, respectively; 7,109,153B 2; 7,071,151B 2; 6,987,084B 2; 6,610,646B 2 and 5,958,870, and can be found in U.S. patent application publications 2005/0003980a1 and 2006/0223726 a 1.

Amine Reaction Product (ARP): for the purposes of this patent application, ARP is a subset or class of PPs. "reactive" polyamines, in which the amine functionality is pre-reacted with one or more PRMs, to form an Amine Reaction Product (ARP), can also be used. Typically the reactive amine is a primary and/or secondary amine and may be part of a polymer or monomer (non-polymer). The ARPs may also be combined with adjunctsThe added PRMs are mixed together to provide polymer assisted delivery and/or amine assisted delivery benefits. Non-limiting examples of polymeric amines include polyalkylimine-based polymers such as Polyethyleneimine (PEI) or polyvinylamine (PVAm). Non-limiting examples of monomeric (non-polymeric) amines include hydroxyl amines, such as 2-aminoethanol and its alkyl substituted derivatives, and aromatic amines, such as anthranilates. The ARPs may be premixed with perfume or added separately in leave-on or rinse-off applications. In another aspect, materials containing heteroatoms other than nitrogen, such as oxygen, sulfur, phosphorus, or selenium, can be used as an alternative amine compound. In yet another aspect, the aforementioned alternative compounds can be used in combination with an amine compound. In yet another aspect, a single molecule can comprise an amine moiety and one or more alternative heteroatom moieties, for example, thiols, phosphines, and selenols. The benefits may include improved delivery of perfume as well as controlled perfume release. Suitable ARP's and methods for preparing the ARP's can be found in U.S. patent application publication 2005/0003980A1 and U.S. patent 6,413,920B 1.

Bleaching agent

The filaments may comprise one or more bleaching agents. Non-limiting examples of suitable bleaching agents include peroxyacids, perborates, percarbonates, chlorine bleaches, bleach powders, hypochlorite bleaches, bleach precursors, bleach activators, bleach catalysts, hydrogen peroxide, bleach boosters, photobleaches, bleaching enzymes, free radical initiators, peroxygen bleaches, and mixtures thereof.

The filaments may comprise one or more bleaching agents at a level of from about 1% to about 30%, and/or from about 5% to about 20%, by weight of the dry filaments and/or on the dry web material. If present, the bleach activator can be present in the filaments at a level of from about 0.1% to about 60%, and/or from about 0.5% to about 40%, by weight of the dry filaments and/or by weight of the dry web material.

Non-limiting examples of bleaching agents include color bleach powders, perborate bleach, percarboxylic acid bleach and salts thereof, peroxygen bleach, persulfate bleach, percarbonate bleach, and mixtures thereof. Further, non-limiting examples of bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S. patent publication 740,446, European patent application 0133354, U.S. Pat. No. 4,412,934, and U.S. Pat. No. 4,634,551.

Non-limiting examples of bleach activators (e.g., acyl lactams) are disclosed in U.S. patent nos. 4,915,854; 4,412, 934; 4,634,551; and 4,966,723.

In one example, the bleaching agent comprises a transition metal bleach catalyst, which may be encapsulated. The transition metal bleach catalyst typically comprises a transition metal ion, for example a transition metal ion from a transition metal selected from: mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (III), and Ru (IV). In one example, the transition metal is selected from: mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Cr (II), Cr (III), Cr (IV), Cr (V), and Cr (VI). The transition metal bleach catalyst typically comprises a ligand, for example a macropolycyclic ligand such as a cross-linked macropolycyclic ligand. The transition metal ion may be complexed with a ligand. Further, the ligand may comprise at least four coordinating atoms, at least two of which are bridgehead coordinating atoms. Non-limiting examples of suitable transition metal bleach catalysts are described in U.S.5,580,485, U.S.4,430,243; U.S.4,728,455; U.S.5,246,621; U.S.5,244,594; U.S.5,284,944; U.S.5,194,416; U.S.5,246,612; U.S.5,256,779; U.S.5,280,117; U.S.5,274,147; U.S.5,153,161; U.S.5,227,084; U.S.5,114,606; U.S.5,114,611, EP 549,271 a 1; EP 544,490a 1; EP 549,272 a 1; and EP 544,440 a 2. In one example, suitable transition metal bleach catalysts include manganese-based catalysts, such as disclosed in U.S. Pat. No.5,576,282. In another example, suitable cobalt bleach catalysts are described in U.S.5,597,936 and U.S.5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as those set forth in U.S.5,597,936 and U.S.5,595,967. In another example, suitable transition metal bleach catalysts include transition metal complexes of ligands such as bispiperidine, as described in WO 05/042532 a 1.

Bleaches other than oxidative bleaches are also known in the art and may be utilized herein (e.g., photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines (U.S. Pat. No. 4,033,718, incorporated herein by reference)), and/or preformed organic peracids such as peroxycarboxylic acids or salts thereof, and/or peroxysulfonic acids or salts thereof. In one example, suitable organic peracids include phthaloylaminoperoxyacetic acid or salts thereof. When present, the photoactivatable bleaching agent, such as a sulfonated zinc phthalocyanine, may be present in the filaments at a level of from about 0.025% to about 1.25% by weight of the dry filaments and/or on the dry material web.

v. whitening agents

Any optical whitening or other whitening or whitening agent known in the art may be incorporated into the filaments in an amount of from about 0.01% to about 1.2% by weight on a dry filament basis and/or on a dry material web basis. Useful commercial optical brighteners can be classified into subclasses which include, but are not necessarily limited to, diphenylethylene, pyrazoline, coumarin, carboxylic acid, methionin, 5-dibenzothiophene dioxide, oxazoles, 5-and 6-membered ring heterocycles, and other miscellaneous agents. Examples of such whitening Agents are disclosed in "the production and Application of Fluorescent whitening Agents", M.Zahradnik, published by John Wiley & Sons, New York (1982). Specific non-limiting examples of optical brighteners for use in the present compositions are those identified in U.S. Pat. No. 4,790,856 and U.S. Pat. No. 3,646,015.

A fabric colorant

The filaments may include a fabric colorant. Non-limiting examples of suitable fabric colorants include small molecule dyes and polymeric dyes. Suitable small molecule dyes include those selected from the group consisting of: belonging to the direct blueDirect red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet, and basic red color index (c.i.) classes of dyes, or mixtures thereof. In another example, suitable polymeric dyes are selected from: by trade mark(Milliken, Spartanburg, South Carolina, USA), a fabric-entity colorant, a dye-polymer conjugate formed from at least one reactive dye, and a polymer selected from the group consisting of polymers comprising: hydroxyl moieties, primary amine moieties, secondary amine moieties, thiol moieties, and mixtures thereof. In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of:(Milliken, Spartanburg, South Carolina, USA) Violet CT, hydroxymethyl CELLULOSE (CMC) conjugated with reactive blue, reactive Violet or reactive red dyes such as CMC conjugated with C.I. reactive blue 19, sold under the product name AZO-CM-CELLULOSE by Megazyme, Wicklow, Ireland, product code S-ACMC, alkoxylated triphenylmethane polymeric colorants, alkoxylated thiophene polymeric colorants and mixtures thereof.

Non-limiting examples of useful hueing dyes include those found in US7,205,269, US7,208,459, and US7,674,757B 2. For example, the fabric hueing dye may be selected from: triarylmethane blue and violet basic dyes, methine blue and violet basic dyes, anthraquinone blue and violet basic dyes, azo dyes basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, basic violet,Oxazine dyes, basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nile blue a and xanthene dyes basic violet 10, alkoxylated triphenylmethane polymer colorants; alkoxylated thiophene polymerizationColorant, thiazoleA dye; and mixtures thereof.

In one example, the fabric hueing dye comprises a brightener, which is present in WO 08/87497 a 1. These whitening agents may be characterized by the following structure (I):

wherein R is₁And R₂Can be independently selected from:

a)[(CH₂CR'HO)_x(CH₂CR″HO)_yH]

wherein R' is selected from: H. CH (CH)₃、CH₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein R' is selected from: H. CH (CH)₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein x + y is less than or equal to 5; wherein y is more than or equal to 1; and wherein z is 0 to 5;

b)R₁alkyl, aryl or aralkyl, and R₂＝[(CH₂CR'HO)_x(CH₂CR″HO)_yH]Wherein R' is selected from: H. CH (CH)₃、CH₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein R' is selected from: H. CH (CH)₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein x

+ y is less than or equal to 10; wherein y is more than or equal to 1; and wherein z is 0 to 5;

c)R₁＝[CH₂CH₂(OR₃)CH₂OR₄]and R is₂＝[CH₂CH₂(O R₃)CH₂O R₄]Wherein R is₃Selected from: H. (CH)₂CH₂O)_zH. And mixtures thereof; and wherein z is 0 to 10;

wherein R is₄Selected from: (C)₁-C₁₆) Alkyl, aryl, and mixtures thereof; and

d) wherein R1 and R2 can be independently selected from the group consisting of amino addition products of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether and glycidyl cetyl ether, followed by addition of 1 to 10 alkylene oxide units.

In another example, a suitable whitening agent can be characterized by the following structure (II):

wherein R' is selected from: H. CH (CH)₃、CH₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein R' is selected from: H. CH (CH)₂O(CH₂CH₂O)_zH. And mixtures thereof; wherein x + y is less than or equal to 5; wherein y is more than or equal to 1; and wherein z is 0 to 5.

In another example, a suitable whitening agent can be characterized by the following structure (III):

such whitening agents are commonly referred to as "violet DD". Violet DD is typically a mixture with a total of 5 EO groups. This structure is obtained by selecting the following pendant groups of structure I as indicated by "part a" above in table I below:

.

R1

R2

R’

R”

X

y

R’

R”

x

y

a

H

3

1

H

0

1

b

H

2

1

H

1

c＝b

H

1

H

2

1

d＝a

H

0

1

H

3

1

TABLE I

Other whitening agents used include those described in US2008/34511 a1 (Unilever). In one example, the whitening agent comprises "violet 13".

Inhibitors of dye transfer

The filaments may include one or more dye transfer inhibiting agents that inhibit the transfer of dye from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10%, and/or from about 0.01% to about 5%, and/or from about 0.05% to about 2%, by weight of the dry filaments and/or by weight of the dry web material.

Chelating agent

The filaments may comprise one or more chelating agents, for example one or more iron, and/or manganese, and/or other metal ion chelating agents. Such chelating agents may be selected from: carbamate salts, aminophosphonate salts, polyfunctional substituted aromatic chelating agents, and mixtures thereof. If used, these chelating agents are present in an amount of from about 0.1% to about 15%, and/or from about 0.1% to about 10%, and/or from about 0.1% to about 5%, and/or from about 0.1% to about 3%, by weight of the dry filaments and/or on the dry material web.

The chelating agent may be selected by one skilled in the art to provide heavy metal (e.g., Fe) chelation without negatively impacting enzyme stability during excessive calcium ion binding. Non-limiting examples of chelating agents are present in US 7445644, US7585376 and US 2009/0176684a 1.

Useful chelators include heavy metal chelators such as diethylenetriaminepentaacetic acid (DTPA) and/or catechol, including but not limited to titanium agents. In various embodiments in which a dual chelator system is used, the chelator can be DTPA and a titanium reagent.

DTPA has the following core molecular structure:

the titanium reagent, also known as 1, 2-dihydroxybenzene-3, 5-disulfonic acid, is a member of the catechol family and has a core molecular structure shown below:

other sulfonated catechols are useful. In addition to disulfonic acid, the term "titanium reagent" may also include mono-or disulfonates of acids, such as the disodium salt of a sulfonic acid, which share the same core molecular structure with disulfonic acid.

Other suitable chelating agents for use herein may be selected from: carbamate salts, aminophosphonate salts, polyfunctional substituted aromatic chelating agents, and mixtures thereof. In one example, chelating agents include, but are not limited to: HEDP (hydroxyethanedimethylenephosphonic acid), MGDA (methylglycinediacetic acid), GLDA (glutamic-N, N-diacetic acid), and mixtures thereof.

Without intending to be bound by theory, it is believed that the beneficial effects of these materials are due in part to their specific ability to remove heavy metal ions from the wash solution by forming soluble chelates; other benefits include inorganic film or peel prevention. Other suitable chelators for use herein are the commercially available DEQUEST series, as well as chelators from Monsanto, DuPont, and Naalco, Inc.

Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetate, N- (hydroxyethyl) ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate, and ethanoldiaminodiacetic acid, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof. Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in the filaments, and include ethylenediamine tetra (methylene phosphonate). In one example, these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Multifunctional substituted aromatic chelating agents may also be used in the compositions herein. See U.S. patent 3,812,044 to Connor et al, published on 21/5/1974. Non-limiting examples of such compounds in acid form are dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

In one example, the biodegradable chelating agent comprises ethylenediamine disuccinate ("EDDS"), e.g., the [ S, S ] isomer, as described in US 4,704,233. The trisodium salt of EDDS can be used. In another example, the magnesium salt of EDDS may also be used.

The one or more chelating agents may be present in the filaments at a level of from about 0.2% to about 0.7%, and/or from about 0.3% to about 0.6% by weight of the dry filaments and/or on the dry material web.

ix, suds suppressors

Compounds for reducing or inhibiting foam formation may be incorporated into the filaments. Suds suppression may be particularly important in so-called "high-intensity cleaning processes" as described in U.S. Pat. nos. 4,489,455 and 4,489,574, and in front loading washing machines.

A wide variety of materials can be used as suds suppressors and suds suppressors are well known to those skilled in the art. See, for example, "Kirk Othmer Encyclopedia of Chemical Technology" third edition, volume 7, page 430-447 (John Wiley)&Sons, inc., 1979). Examples of suds suppressors include monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀Ketones (e.g., stearyl ketone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point of less than about 100 ℃, silicone suds suppressors, and secondary alcohols. Suds suppressors are described in U.S. Pat. nos. 2,954,347; 4,265,779, respectively; 4,265,779, respectively; 3,455,839; 3,933,672; 4,652,392; 4,978,471, respectively; 4,983,316, respectively; 5,288,431, respectively; 4,639,489, respectively; 4,749,740, respectively; and 4,798,679; 4,075,118, respectively; european patent application 89307851.9; EP 150,872; and DOS 2,124,526.

For any filament and/or nonwoven fabric comprising such filaments designed for use in an automatic washing machine, foam should not form that overflows the washing machine. When used, the amount of suds suppressor present is preferably a "suds suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition is able to select the amount of such suds controlling agent that will be sufficient to control suds to produce a low sudsing laundry detergent for use in an automatic washing machine.

The filaments herein will generally comprise from 0% to about 10% of a suds suppressor, on a dry filament basis and/or by weight of the dry web material. When used as suds suppressors, for example, the amount of monobasic fatty acid and salts thereof can be up to about 5%, and/or from about 0.5% to about 3%, by weight on a dry filament basis and/or on a dry web material. When utilized, silicone suds suppressors are typically employed in the filaments at levels up to about 2.0% by weight, based on dry filament and/or dry material web weight, although higher amounts can be used. When utilized, the monostearyl phosphate suds suppressors typically used for filaments are present in amounts of from about 0.1% to about 2% by weight, based on dry filament and/or dry material web. When utilized, hydrocarbon suds suppressors are typically employed in the filaments at levels of from about 0.01% to about 5.0% by weight on a dry filament basis and/or dry material web basis, although higher levels may be used. When utilized, alcohol suds suppressors typically employed in the filaments are present in an amount of from about 0.2% to about 3% by weight, based on the dry filaments and/or on the dry material web.

x. foam promoter

If high foaming is desired, a foam booster such as C can be used₁₀-C₁₆The alkanolamides are incorporated into the filaments generally at levels of from 0% to about 10%, and/or from about 1% to about 10%, by weight of the dry filaments and/or by weight of the dry web material. C₁₀-C₁₄Monoethanol and diethanolamide illustrate a typical class of such suds boosters. The use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines mentioned above is also advantageous. If desired, water-soluble magnesium and/or calcium salts such as MgCl can be added₂、MgSO₄、CaCl₂、CaSO₄And the like are added to provide additional foam in an amount of from about 0.1% to about 2% on a dry filament basis and/or on a dry web material weight basis.

xi. softening agent

One or more softeners may be present in the filaments. Non-limiting examples of softening agents include quaternary ammonium compounds such as quaternary ammonium ester compounds, silicones such as polysiloxanes, clays such as smectite clays, and mixtures thereof.

In one example, the softener comprises a fabric softener. Non-limiting examples of fabric softeners include intangible smectites such as those described in U.S.4,062,647, and other fabric softeners known in the art. When present, the fabric softener may be present in the filaments at a level of from about 0.5% to about 10%, and/or from about 0.5% to about 5%, by weight of the dry filaments and/or on the dry web material. The fabric softening clay may be used in combination with an amine and/or a cationic softener such as those disclosed in U.S.4,375,416 and U.S.4,291,071. Cationic softeners may also be used without the fabric softening clay.

Conditioner

The filaments may include one or more conditioning agents such as high melting point fatty compounds. The high melting point fatty compound may have a melting point of about 25 ℃ or more and may be selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Such fatty compounds exhibiting a low melting point (less than 25 ℃) are not intended to be included as conditioning agents. Non-limiting examples of high melting point fatty compounds can be found in 1993 "International Cosmetic ingredient dictionary" fifth edition; and in 1992 "CTFA Cosmetic Ingredient Handbook", second edition.

The one or more high melting point fatty compounds may be included in the filaments at a level of from about 0.1% to about 40%, and/or from about 1% to about 30%, and/or from about 1.5% to about 16%, and/or from about 1.5% to about 8% by weight of the dry filaments and/or on the dry material web. The conditioning agents can provide conditioning benefits such as slippery feel of wet hair and/or fabric, softness and/or moisturized feel of dry hair and/or fabric produced during application.

The filaments may comprise a cationic polymer as a conditioning agent. When present, the concentration of the cationic polymer in the filaments typically ranges from about 0.05% to about 3%, and/or from about 0.075% to about 2.0%, and/or from about 0.1% to about 1.0% by weight of the dry filaments and/or on the dry web material. Non-limiting examples of suitable cationic polymers can have a cationic charge density of at least 0.5meq/gm, and/or at least 0.9meq/gm, and/or at least 1.2meq/gm, and/or at least 1.5meq/gm at a pH of about 3 to about 9, and/or about 4 to about 8. In one example, cationic polymers suitable for use as conditioning agents may have a cationic charge density of less than 7meq/gm, and/or less than 5meq/gm at a pH of from about 3 to about 9, and/or from about 4 to about 8. The "cationic charge density" of a polymer herein refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The weight average molecular weight of such suitable cationic polymers is generally between about 10,000 and 1 million, in one embodiment between about 50,000 and about 5 million, and in another embodiment between about 100,000 and about 3 million.

Suitable cationic polymers for the filaments may comprise cationic nitrogen-containing moieties such as quaternary ammonium and/or cationic protonated amino moieties. Any anionic counterions can be used in conjunction with the cationic polymers so long as the cationic polymers remain soluble in water and so long as the counterions are physically and chemically compatible with the other components of the filament or otherwise do not unduly impair filament performance, stability or aesthetics. Non-limiting examples of such counterions include halide (e.g., chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

Non-limiting examples of such cationic polymers are described in CTFAComatic Ingredient Dictionary, 3 rd edition, by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)).

Other suitable cationic polymers for such filaments may include cationic polysaccharide polymers, cationic guar derivatives, quaternary nitrogen containing cellulose ethers, cationic synthetic polymers, cationic copolymers of etherified cellulose, guar and starch. When used, the cationic polymers herein can be dissolved in water. Further, suitable cationic polymers for filaments are described in U.S.3,962,418, U.S.3,958,581, and U.S.2007/0207109a1, all of which are incorporated herein by reference.

The filaments may include a nonionic polymer as a conditioning agent. Polyalkylene glycols having a molecular weight in excess of about 1000 are used herein. Useful are those having the general formula:

wherein R is⁹⁵Selected from: hydrogen, methyl, and mixtures thereof.

The filaments may include silicone as a conditioning agent. Silicones used as conditioning agents typically comprise a water-insoluble, water-dispersible, non-volatile liquid that forms emulsified liquid particles. Suitable conditioning agents for use in the compositions are those conditioning agents characterized generally as silicones (e.g., silicone oils, cationic silicones, silicone gums, highly refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty acid esters), or combinations thereof, or otherwise forming liquid dispersed particles in the aqueous surfactant matrix herein. Such conditioning agents should be physically and chemically compatible with the essential components of the composition and not unduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the filament can be sufficient to provide the desired hair care benefits. Such concentrations may vary with the conditioner, the desired conditioning performance, the average size of the conditioner particles, the type and concentration of other components, and other similar factors.

The concentration of silicone conditioning agent is typically in the range of from about 0.01% to about 10% by weight on a dry filament basis and/or on a dry web material basis. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicones are described in U.S. reissue patent 34,584, U.S. patent 5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837; 6,607,717, respectively; 6,482,969, respectively; 5,807,956, respectively; 5,981,681, respectively; 6,207,782, respectively; 7,465,439, respectively; 7,041,767, respectively; 7,217,777, respectively; U.S. patent application 2007/0286837a 1; 2005/0048549A 1; 2007/0041929A 1; british patents 849,433; german patent DE 10036533, the above-mentioned patent documents all being incorporated herein by reference; "Chemistry and Technology of Silicones" (New York: Academic Press, 1968); general Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76; "Silicon Compounds" (Petrarch Systems, Inc., 1984); and "Encyclopedia of Polymer Science and Engineering", second edition, Vol.15, p.204-308 (John Wiley & Sons, Inc., 1989).

In one example, the filaments may also comprise from about 0.05% to about 3%, by weight of the dry filaments and/or on the dry web material, of at least one organic conditioning oil as a conditioning agent, either alone or in combination with other conditioning agents such as silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters. Also suitable for use in the compositions herein are the conditioning agents described by Procter & Gamble Company in U.S. Pat. Nos. 5,674,478 and 5,750,122. Those conditioning agents described in U.S. Pat. Nos. 4,529,586, 4,507,280, 4,663,158, 4,197,865, 4,217,914, 4,381,919, and 4,422,853, all of which are incorporated herein by reference, are also suitable for use herein.

xiii wetting agent

The filaments may comprise one or more humectants. The wetting agent herein is selected from the group consisting of polyols, water-soluble alkoxylated nonionic polymers, and mixtures thereof. When used, the humectant can be present in the filaments at a level of from about 0.1% to about 20%, and/or from about 0.5% to about 5%, by weight of the dry filaments and/or on the dry material web.

xiv. suspending agent

The filaments may further comprise a suspending agent in a concentration effective for suspending the water-insoluble material in the composition in dispersed form or for adjusting the viscosity of the composition. Such concentrations of suspending agent range from about 0.1% to about 10%, and/or from about 0.3% to about 5.0% by weight on a dry filament basis and/or on a dry web material basis.

Non-limiting examples of suitable suspending agents include anionic polymers and nonionic polymers (e.g., polyvinyl resin polymers, acyl derivatives, long chain amine oxides, and mixtures thereof, alkanolamines of fatty acids, long chain esters of long chain alkanolamines, glycerol esters, primary amines having a fatty alkyl moiety of at least about 16 carbon atoms, secondary amines having two fatty alkyl moieties of at least about 12 carbon atoms). Examples of suspensions are described in U.S. Pat. No. 4,741,855.

xv. enzyme

One or more enzymes may be present in the filament. Non-limiting examples of suitable enzymes include proteases, amylases, lipases, cellulases, carbohydrases, including mannanases and endoglucanases, pectinases, hemicellulases, peroxidases, xylanases, phospholipases, esterases, cutinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mailanases, glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and mixtures thereof.

Enzymes may be included in filaments for a variety of uses including, but not limited to, the removal of protein-based stains, carbohydrate-based stains, or triglyceride-based stains from substrates, for the prevention of dye transfer in fabric washing, and for fabric repair. In one example, the filaments can include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, such as plant, animal, bacterial, fungal, and yeast origin. The choice of enzyme to be utilized is influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to other additives present in the filament, such as active agents, e.g. builders. In one example, the enzyme is selected from the group consisting of: bacterial enzymes (e.g., bacterial amylases and/or bacterial proteases), fungal enzymes (e.g., fungal cellulases), and mixtures thereof.

When present in the filament, the enzyme may be present in an amount sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness-improving effect on a substrate, such as fabric, dish, or the like. Indeed, typical amounts for current commercial preparations are up to about 5mg, more typically 0.01mg to 3mg, by weight of active enzyme per gram of filaments and/or fibres. In other words, the filaments may typically comprise from about 0.001% to about 5%, and/or from about 0.01% to about 3%, and/or from about 0.01% to about 1% enzyme by weight on a dry filament basis and/or on a dry web material basis.

After the filament and/or fibrous structure is prepared, one or more enzymes may be applied to the filament and/or fibrous structure.

The range of enzyme materials and their means of incorporation into the filament-forming composition (which may be a synthetic detergent composition) are also disclosed in the following documents: WO 9307263A; WO 9307260A; WO 8908694A; us patent 3,553,139; 4,101,457, respectively; and us patent 4,507,219.

An enzyme stabilizing system

When an enzyme is present in the filament and/or fiber, the filament may also include an enzyme stabilizing system. Enzymes can be stabilized by a variety of techniques. Non-limiting examples of enzyme stabilization techniques are disclosed and exemplified in the following documents: U.S. Pat. nos. 3,600,319 and 3,519,570; EP 199,405, EP 200,586 and WO 9401532 a.

In one example, the enzyme stabilizing system may comprise calcium and/or magnesium ions.

The enzyme stabilizing system may be present in the filaments at a level of from about 0.001% to about 10%, and/or from about 0.005% to about 8%, and/or from about 0.01% to about 6% by weight of the dry filaments and/or on the dry material web. The enzyme stabilizing system may be any stabilizing system compatible with the enzyme present in the filament. Such enzyme stabilizing systems may be provided automatically by the other formulation active or added separately, for example by the formulator or producer of the enzyme. Such enzyme stabilizing systems may, for example, include calcium ions, magnesium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof, and are designed to address different stabilization issues.

xvii. builder

The filament may comprise one or more builders. Non-limiting examples of suitable builders include zeolite builders, aluminosilicate builders, silicate builders, phosphate builders, citric acid, citrate, nitrilotriacetic acid, polyacrylates, acrylate/maleate copolymers, and mixtures thereof.

In one example, a builder may be included in the filament, the builder being selected from: aluminosilicates, silicates, and mixtures thereof. Builders can be included in the filaments herein to aid in controlling mineral, especially calcium and/or magnesium hardness in wash water, or to aid in the removal of particulate soils from surfaces. Also suitable for use herein are synthetic crystalline ion exchange materials, or hydrates thereof, having a chain structure and a component represented by the general formula I in the form of the following anhydride: x (M)₂O)·ySiO₂·zM'O，Wherein M is Na and/or K, and M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as proposed in us patent 5,427,711.

Non-limiting examples of other suitable builders that the filaments may include phosphates and polyphosphates such as their sodium salts; carbonate, bicarbonate, sesquicarbonate and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylic acid salts, such as water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types of carboxylates; and phytic acid. These builders may be supplemented with borates, e.g. for pH buffering purposes, or with sulfates, e.g. sodium sulfate and any other fillers or carriers, which may be important for the engineering of stable surfactants and/or builder-containing filaments.

Other builders can be selected from polycarboxylates, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and/or maleic acid with other suitable alkenyl monomers having various types of additional functions.

Builder levels can vary widely depending on the end use. In one example, the filaments may comprise at least 1%, and/or from about 1% to about 30%, and/or from about 1% to about 20%, and/or from about 1% to about 10%, and/or from about 2% to about 5% of one or more builders by weight of dry filaments.

Clay soil removal/anti-redeposition agent

The filaments may comprise water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. The level of such water-soluble ethoxylated amines in the filaments is from about 0.01% to about 10.0%, and/or from about 0.01% to about 7%, and/or from about 0.1% to about 5% by weight of one or more water-soluble ethoxylated amines on a dry filament basis and/or dry web material basis. Non-limiting examples of suitable clay soil removal/anti-redeposition agents are described in U.S. patent 4,597,898; 548,744, respectively; 4,891,160, respectively; european patent application 111,965; 111,984, respectively; 112,592, respectively; and in WO 95/32272.

x. polymeric detergents

The filaments may comprise a polymeric detergent, hereinafter referred to as "SRA". If utilized, the amount of SRA will generally be from about 0.01% to about 10.0%, and/or from about 0.1% to about 5%, and/or from about 0.2% to about 3.0% by weight on a dry filament basis and/or on a dry web material basis.

SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyesters and nylons, and hydrophobic segments to deposit on and remain adhered to hydrophobic fibers until the wash and rinse cycles are complete, thereby acting as an anchor for the hydrophilic segments. This allows stains that appear after treatment with SRA to be more easily removed later in the washing process.

SRAs may include, for example, a variety of charged, e.g., anionic or even cationic (see U.S. patent publication 4,956,447), and uncharged monomer units, and the structures may be linear, branched, or even star-shaped. They may include end-capping moieties that are particularly effective in controlling molecular weight or modifying physical or surface active properties. The structure and charge distribution can be determined for different fiber or textile types and different detergent or detergent auxiliary products. Non-limiting examples of SRAs are described in us patent 4,968,451; 4,711,730, respectively; 4,721,580, respectively; 4,702,857, respectively; 4,877,896, respectively; 3,959,230; 3,893,929; 4,000,093, respectively; 5,415,807, respectively; 4,201,824, respectively; 4,240,918, respectively; 4,525,524, respectively; 4,201,824, respectively; 4,579,681, respectively; and 4,787,989; european patent application 0219048; 279,134A; 457,205A; and DE 2,335,044.

xx. polymeric dispersant

Polymeric dispersants may be advantageously employed in the filaments at levels of from about 0.1% to about 7%, and/or from about 0.1% to about 5%, and/or from about 0.5% to about 4%, by weight of the dry filaments and/or on the dry material web, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants may include polymeric polycarboxylates and polyethylene glycols, however, other polymeric dispersants known in the art may also be used. For example, a wide variety of modified or unmodified polyacrylates, polyacrylate/maleates, or polyacrylate/methacrylates are highly useful. While not intending to be limited by theory, it is believed that the polymeric dispersants, when used in combination with other builders (including lower molecular weight polycarboxylates), enhance the overall performance of the detergent builder by crystal growth inhibition, granular detergent debonding, and anti-redeposition. Non-limiting examples of polymeric dispersants are found in U.S. patent publication 3,308,067, European patent application 66915, EP 193,360 and EP 193,360.

Alkoxylated polyamine polymers

The filaments may include alkoxylated polyamines for providing soil suspension, grease cleaning, and/or particle cleaning. Such alkoxylated polyamines include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylene diamine, and sulfates thereof. The filaments may also include polypropoxylated derivatives of polyamines. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees and optionally also modified to provide the benefits described above. A useful example is a 600g/mol polyethyleneimine core ethoxylated to 20EO groups/NH and available from BASF.

xxii. alkoxylated polycarboxylate polymers

Alkoxylated polycarboxylates such as those prepared from polyacrylates may be included in the filaments to provide additional grease removal properties. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials comprise polyacrylates having an ethoxy side chain every 7-8 acrylate units. The side chain is of the formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2-3 andand n is 6 to 12. The side chains are linked to the polyacrylate "backbone" via ester linkages to provide a "comb polymer" structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can be present from about 0.05% to about 10% by weight on a dry filament basis and/or on a dry web material.

xxiii. amphiphilic graft copolymer

The filaments may comprise one or more amphiphilic graft copolymers. Examples of suitable amphiphilic graft copolymers include (i) a polyethylene glycol backbone; and (ii) at least one pendant moiety selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. A non-limiting example of a commercially available amphiphilic graft copolymer is Sokalan HP22, available from BASF.

xxiv. dissolution aid

When the filaments contain more than 40% surfactant or surfactant composition for use in cold water, the filaments of the present invention may incorporate a dissolution aid to accelerate dissolution and thereby reduce the formation of insoluble or low-solubility surfactant aggregates (which may sometimes form). Non-limiting examples of dissolution aids include sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, magnesium chloride, and magnesium sulfate.

xxv.Buffer system

The filaments may be formulated such that during use in an aqueous cleaning operation, such as washing clothes or dishes, the wash water will have a pH of between about 5.0 and about 12, and/or between about 7.0 and 10.5. In the case of a dishwashing operation, the pH of the wash water is typically between about 6.8 and about 9.0. In the case of laundry washing, the pH of the wash water is typically between 7 and 11. Techniques for adjusting the pH to a desirable use level include the use of buffers, bases, acids, and the like, and are well known to those skilled in the art. These include the use of sodium carbonate, citric acid or sodium citrate, monoethanolamine or other amines, boric acid or borates, and other pH adjusting compounds well known in the art.

Filaments for use as "low pH" detergent compositions may be included and are particularly suitable for use in surfactant systems and may provide an application pH of less than 8.5, and/or less than 8.0, and/or less than 7.0, and/or less than 5.5, and/or to about 5.0.

May include in-wash dynamic pH profile filaments. Such filaments may be treated with wax-covered citric acid particles and other pH control agents such that (i) after 3 minutes of contact with water, the pH of the wash liquor is greater than 10; (ii) after 10 minutes of contact with water, the pH of the wash liquor is less than 9.5; (iii) after 20 minutes of contact with water, the pH of the wash liquor is less than 9.0; and (iv) optionally, wherein the equilibrium pH of the wash liquor is in the range of from above 7.0 to 8.5.

xxvi. thermoforming agent

The filaments may comprise a thermoformer. The heat-forming agent is formulated to generate heat in the presence of water and/or oxygen (e.g., oxygen in the air, etc.), and thereby accelerate the rate at which the fibrous structure degrades in the presence of water and/or oxygen, and/or increase the effectiveness of one or more active substances in the filament. The thermoforming agent may also or alternatively be used to accelerate the rate of release of one or more active substances from the fibrous structure. The heat forming agent is formulated to react exothermically upon exposure to oxygen (i.e., oxygen in air, oxygen in water) and/or water. Many different materials and combinations of materials may be used as the thermoforming agent. Non-limiting heat forming agents that can be used in the fibrous structure include electrolyte salts (e.g., aluminum chloride, calcium sulfate, copper chloride, cuprous chloride, ferric sulfate, magnesium chloride, magnesium sulfate, manganese chloride, manganese sulfate, potassium chloride, potassium sulfate, sodium acetate, sodium chloride, sodium carbonate, sodium sulfate, etc.), glycols (e.g., propylene glycol, dipropylene glycol, etc.), lime (e.g., quick lime, slaked lime, etc.), metals (e.g., chromium, copper, iron, magnesium, manganese, etc.), metal oxides (e.g., aluminum oxide, iron oxide, etc.), polyalkyleneamines, polyalkyleneimines, polyethyleneamines, zeolites, glycerol, 1,3, propylene glycol, polysorbates (e.g., tween 20, 60, 85, 80), and/or polyglycerol esters (e.g., Noobe, Drewpol, and Drewmulze from Stepan). The thermoformer may be formed from one or more materials. For example, magnesium sulfate alone may form the thermal former. In another non-limiting example, a combination of about 2-25 wt% activated carbon, about 30-70 wt% iron powder, and about 1-10 wt% metal salt may form the thermoformer. As can be appreciated, other or additional materials may be used alone or in combination with other materials to form the thermal forming agent. Non-limiting examples of materials that can be used to form a thermoformer for use in a fibrous structure are disclosed in U.S. Pat. nos. 5,674,270 and 6,020,040; and U.S. patent application publications 2008/0132438 and 2011/0301070.

xxvii. degradation promoters

The filaments may comprise a degradation promoting agent for increasing the rate at which the fibrous structure degrades in the presence of water and/or oxygen. When used, the degradation promoting agent is generally designed to release a gas when exposed to water and/or oxygen, which in turn agitates the area surrounding the fibrous structure to accelerate degradation of the carrier film of the fibrous structure. When used, the degradation promoter may also or alternatively be used to accelerate the rate of release of one or more active substances from the fibrous structure; however, this is not essential. When used, the degradation promoter may also or alternatively be used to increase the effect of one or more active substances in the fibrous structure; however, this is not essential. The degradation promoter may include one or more substances such as, but not limited to, alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (e.g., sodium bicarbonate, potassium bicarbonate, etc.), ammonium carbonate, and the like. The water-soluble strip may optionally include one or more activators that may be used to activate or increase the rate of activation of the one or more degradation-promoting agents in the fibrous structure. As can be appreciated, one or more activating agents may be included in the fibrous structure even when no degradation promoting agent is present in the fibrous structure; however, this is not essential. For example, the activator may comprise an acidic or basic compound, wherein such acidic or basic compound may act as a supplement to one or more active substances in the fibrous structure when a degradation-promoting agent is included or excluded from the fibrous structure. Non-limiting examples of activators that can be included in the fibrous structure, when used, include organic acids (e.g., hydroxy-carboxylic acids [ citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, and the like ], saturated aliphatic carboxylic acids [ acetic acid, succinic acid, and the like ], unsaturated aliphatic carboxylic acids [ e.g., fumaric acid, and the like ] non-limiting examples of materials that can be used to form degradation promoters and activators for use in the fibrous structure are disclosed in U.S. patent application publication 2011/0301070.

Release of active Agents

The filament may release one or more active agents when the filament is exposed to a triggering condition. In one example, the filament or portion of the filament may release one or more active agents when the filament or portion of the filament loses its identity, in other words, loses its physical structure. For example, a filament loses its physical structure when the filament-forming material dissolves, melts, or undergoes some other transformation step such that the filament structure is lost. In one example, the filament releases one or more active agents when the morphology of the filament is altered.

In another example, a filament or portion of a filament may release one or more active agents when the filament or portion of the filament changes its identity, in other words, changes its physical structure rather than losing its physical structure. For example, a filament changes its physical structure as the filament-forming material swells, crumples, lengthens, and/or shortens, but retains its filament-forming characteristics.

In another example, the morphology of the filaments does not change (without losing or changing their physical structure), and the filaments may release one or more active agents.

In one example, the filament may release the active agent when the filament is exposed to a triggering condition that results in the release of the active agent, e.g., causes the filament to lose or change its identity as described above. Non-limiting examples of trigger conditions include exposing the filaments to a solvent, a polar solvent such as alcohol and/or water, and/or a non-polar solvent, which may be continuous, depending on whether the filament-forming material comprises a polar solvent-soluble material and/or a non-polar solvent-soluble material; exposing the filament to heat, for example to a temperature greater than 75 ° f, and/or greater than 100 ° f, and/or greater than 150 ° f, and/or greater than 200 ° f, and/or greater than 212 ° f; exposing the filaments to cooling, such as to a temperature of less than 40 ° f, and/or less than 32 ° f, and/or less than 0 ° f; exposing the filaments to a stress, such as a stretching force applied by a consumer using the filaments; and/or exposing the filaments to a chemical reaction; exposing the filaments to conditions that cause a phase change; exposing the filaments to a change in pH, and/or a change in pressure, and/or a change in temperature; exposing the filament to one or more chemical agents that cause the filament to release one or more of its active agents; exposing the filaments to ultrasonic welding; exposing the filaments to light and/or certain wavelengths; exposing the filaments to different ionic strengths; and/or exposing the filament to an active agent released from another filament.

In one example, the filaments may release one or more active agents when the nonwoven web comprising the filaments is subjected to a triggering step selected from the group consisting of: pretreating a stain on a fabric article with a nonwoven web; forming a wash liquor by contacting the nonwoven web with water; drying the nonwoven web in a dryer; heating the nonwoven web in a dryer; and combinations thereof.

Filament-forming composition

The filaments may be made from a filament-forming composition. The filament-forming composition may be a polar solvent-based composition. In one example, the filament-forming composition may be an aqueous composition comprising one or more filament-forming materials and one or more active agents.

When filaments are prepared from the filament-forming composition, the filament-forming composition may be processed at a temperature of from about 50 ℃ to about 100 ℃, and/or from about 65 ℃ to about 95 ℃, and/or from about 70 ℃ to about 90 ℃.

In one example, the filament-forming composition may comprise at least 20%, and/or at least 30%, and/or at least 40%, and/or at least 45%, and/or at least 50% to about 90%, and/or to about 85%, and/or to about 80%, and/or to about 75% by weight of one or more filament-forming materials, one or more active agents, and mixtures thereof. The filament-forming composition may comprise from about 10% to about 80% by weight of a polar solvent, such as water.

The filament-forming composition may exhibit a capillary number of at least 1, and/or at least 3, and/or at least 5, such that the filament-forming composition can be efficiently polymer-processed into hydroxyl polymer fibers.

The capillary number is a dimensionless number used to characterize the likelihood of such a droplet breaking. A larger capillary number indicates more stability of the fluid as it exits the die. The capillary number is defined as follows:

v is the fluid velocity (in length per time) at the die exit,

η is the viscosity of the fluid at the die conditions (units are mass per length time),

σ is the surface tension of the fluid (unit is mass per time)²). When speed, viscosity and surface tension are expressed as a set of uniform units, the resulting capillary number will not have its own units; the respective units may cancel.

The capillary number is defined for the conditions at the orifice. The fluid velocity is the average velocity of the fluid flowing through the die exit. The average speed is defined as follows:

vol ═ volumetric flow (unit is length)³Time)

Area is the cross-sectional Area (length in units) at the die exit²)。

When the die opening is a circular hole, then the flow velocity can be defined as follows

R is the circular hole radius (unit is length).

The fluid viscosity will depend on the temperature and may depend on the shear rate. The definition of shear-thinning fluid includes dependence on shear rate. The surface tension will depend on the fluid composition and the fluid temperature.

In the fiber spinning process, the filaments need to have initial stability as they exit the die. The capillary number is used to characterize this initial stability criterion. Under the conditions of the die, the capillary number should be greater than 1 and/or greater than 4.

In one example, the filament-forming composition exhibits a capillary number of at least 1 to about 50, and/or at least 3 to about 50, and/or at least 5 to about 30.

In one example, the filament-forming composition may comprise one or more release agents and/or lubricants. Non-limiting examples of suitable release agents and/or lubricants include fatty acids, fatty acid salts, fatty alcohols, fatty acid esters, sulfonated fatty acid esters, acetic acid fatty amines and fatty acid amides, silicones, aminosilicones, fluoropolymers, and mixtures thereof.

In one example, the filament-forming composition may comprise one or more anti-blocking and/or anti-blocking agents. Non-limiting examples of suitable antiblocking and/or antiblocking agents include starch, modified starch, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silicon dioxide, metal oxides, calcium carbonate, talc and mica.

The active agent may be added to the filament-forming composition before and/or during filament formation and/or may be added to the filament after filament formation. For example, the perfume active agent may be applied to the filaments and/or nonwoven web comprising the filaments after the filaments and/or nonwoven web are formed. In another example, the enzymatic active agent can be applied to the filaments and/or nonwoven web comprising the filaments after the filaments and/or nonwoven web are formed. In another example, one or more particulate active agents, such as one or more ingestible active agents, such as bismuth subsalicylate (which may not be suitable for use in making filaments by a spinning process), may be applied to the filaments and/or the nonwoven web comprising the filaments after the filaments and/or nonwoven web are formed.

V. Process for producing filaments

The filaments may be prepared by any suitable method. Non-limiting examples of suitable processes for making filaments are described below.

In one example, a method for making a filament includes the steps of: a. providing a filament-forming composition comprising one or more filament-forming materials and one or more active agents; spinning a filament-forming composition into one or more filaments comprising one or more filament-forming materials and one or more active agents that are releasable from the filament when the filament is exposed to conditions of intended use, wherein the total level of the one or more filament-forming materials present in the filament is less than 65% and/or 50% or less by weight on a dry filament basis and/or on a dry detergent product basis, and the total level of the one or more active agents present in the filament is greater than 35% and/or 50% or more by weight on a dry filament basis and/or on a dry detergent product basis.

In one example, when forming the filaments, any volatile solvent, such as water, present in the filament-forming composition is removed during the spinning step, such as by drying. In one example, greater than 30%, and/or greater than 40%, and/or greater than 50% by weight of the volatile solvent of the filament-forming composition, such as water, is removed during the spinning step, e.g., by drying the resulting filaments.

The filament-forming composition may comprise any suitable amount of filament-forming material and any suitable amount of active agent, provided that the filaments produced from the filament-forming composition comprise filaments having a total content of filament-forming material in the filaments of from about 5% to 50% or less by weight on a dry filament basis and/or on a dry detergent product basis and a total content of active agent in the filaments of from 50% to about 95% by weight on a dry filament basis and/or on a dry detergent product basis.

In one example, the filament-forming composition can comprise any suitable amount of filament-forming material and any suitable amount of active agent, wherein the weight ratio of filament-forming material to additive is 1 or less, provided that the filaments produced from the filament-forming composition comprise filaments having a total content of filament-forming material in the filaments of about 5% to 50% or less, based on dry filament and/or on dry detergent product weight, and a total content of active agent in the filaments of 50% to about 95%, based on dry filament and/or on dry detergent product weight.

In one example, the filament-forming composition comprises from about 1%, and/or from about 5%, and/or from about 10% to about 50%, and/or to about 40%, and/or to about 30%, and/or to about 20%, by weight of the filament-forming composition, of a filament-forming material; from about 1%, and/or from about 5%, and/or from about 10% to about 50%, and/or to about 40%, and/or to about 30%, and/or to about 20%, by weight of the filament-forming composition, of an active agent; and about 20%, and/or about 25%, and/or about 30%, and/or about 40% and/or to about 80%, and/or to about 70%, and/or to about 60%, and/or to about 50%, by weight of the filament-forming composition, of a volatile solvent, such as water. The filament-forming composition may contain minor amounts of other active agents, such as less than 10%, and/or less than 5%, and/or less than 3%, and/or less than 1% by weight of the filament-forming composition of plasticizers, pH adjusters, and other active agents.

The filament-forming composition is spun into one or more filaments by any suitable spinning process, such as melt-blowing and/or spunbonding. In one example, the filament-forming composition is spun into a plurality of filaments by a melt-blowing process. For example, the filament-forming composition may be pumped from an extruder into a melt-blowing spinneret. The filament-forming composition is attenuated with air as the one or more filaments exiting the spinneret form the cavities, thereby producing one or more filaments. The filaments may then be dried to remove any residual solvent, such as water, used for spinning.

The filaments can be collected on a molding member, such as a patterned belt, to form a fibrous structure.

Detergent products, VI

Detergent products comprising one or more active agents exhibit new properties, characteristics, and/or combinations thereof as compared to known detergent products comprising one or more active agents.

A. Fiber structure

In one example, the detergent product may comprise a fibrous structure, such as a fibrous web. One or more, and/or a plurality of filaments may be formed into a fibrous structure by any suitable method known in the art. The fibrous structure can be used to deliver an active agent from the filaments when the fibrous structure is exposed to the filaments and/or the conditions of intended use of the fibrous structure.

Although the fibrous structure may be in solid form, the filament-forming composition used to prepare the filaments may be in liquid form.

In one example, the fibrous structure may comprise a plurality of filaments that are compositionally identical or substantially identical. In another example, the fibrous structure may comprise two or more different filaments. Non-limiting examples of filament differences may be physical differences such as differences in diameter, length, texture, shape, stiffness, elasticity, etc.; chemical differences such as level of crosslinking, solubility, melting point, Tg, active agent, filament-forming material, color, active agent content, filament-forming material content, presence or absence of any coating on the filament, biodegradability or not, hydrophobicity or not, contact angle, and the like; whether the filaments lose their difference in physical structure when exposed to conditions of intended use; differences in whether the filaments change morphology when exposed to conditions of intended use; and the difference in the rate at which the filament releases one or more of its active agents when exposed to conditions of intended use. In one example, two or more filaments within a fibrous structure may comprise the same filament-forming material, but with different active agents. This may be the case where different actives may be incompatible with each other, for example anionic surfactants (such as shampoo actives) and cationic surfactants (such as hair conditioner actives).

In another example, the fibrous structure may comprise two or more different layers (in the Z-direction of the fibrous structure of the filaments forming the fibrous structure) the filaments in a layer may be the same or different from the filaments of another layer. Each layer may comprise a plurality of the same or substantially the same or different filaments. For example, a filament that can release its active agent at a faster rate than other filaments within the fibrous structure may be positioned at the outer surface of the fibrous structure.

In another example, the fibrous structure may exhibit different regions, such as regions of different basis weight, density, and/or thickness. In another example, the fibrous structure may comprise a texture on one or more surfaces thereof. The surface of the fibrous structure may comprise a pattern such as a non-random repeating pattern. The fibrous structure may be embossed with an embossing pattern. In another example, the fibrous structure may contain pores. The holes may be arranged in a randomly repeating pattern.

In one example, the fibrous structure may comprise discrete regions of filaments that are distinct from other portions of the fibrous structure.

Non-limiting examples of uses for fibrous structures include, but are not limited to, laundry dryer substrates, washing machine substrates, bath towels, hard surface cleaning and/or polishing substrates, floor cleaning and/or polishing substrates, as battery components, baby wipes, adult wipes, feminine hygiene wipes, toilet paper wipes, window cleaning substrates, oil inhibitor and/or oil scavenger substrates, insect repellant substrates, swimming pool chemical substrates, food products, breath fresheners, deodorants, garbage disposal bags, packaging films and/or wraps, wound dressings, drug delivery, building insulation, crop and/or plant coverings and/or placements, glue substrates, skin care substrates, hair care substrates, air care substrates, water treatment substrates and/or filters, toilet bowl cleaning substrates, candy substrates, laundry and/or laundry, Pet food, livestock bedding, tooth whitening substrates, carpet cleaning substrates, and other suitable uses of active agents.

The fibrous structure may be used as such or may be coated with one or more active agents.

In another example, the fibrous structure can be pressed into a film, for example by applying a compressive force and/or heating the fibrous structure to convert the fibrous structure into a film. The film will contain the active agent present in the filaments. The fibrous structure may be completely converted into a film, or a portion of the fibrous structure may remain in the film after the fibrous structure is partially converted into a film. The film may be used for any suitable purpose, and the use of the active agent may include, but is not limited to, the use exemplified by the fibrous structure.

B. Method of using a detergent product

Nonwoven webs or films comprising one or more fabric care actives may be utilized in a process for treating fabric articles. The method of treating a fabric article may comprise one or more steps selected from: (a) pretreating said fabric article prior to washing said fabric article; (b) contacting the fabric article with a wash liquor formed by contacting the nonwoven web or film with water; (c) contacting the fabric article with the nonwoven web or film in a dryer; (d) drying the fabric article in the presence of the nonwoven web or film in a dryer; and (e) combinations thereof.

In some embodiments, the method may further comprise the step of pre-wetting the nonwoven web or film prior to contacting it with the fabric article to be pretreated. For example, a nonwoven web or film can be pre-wetted with water and then adhered to a portion of the fabric containing the stain to be pretreated. Alternatively, the fabric may be moistened and a web or film placed on or adhered to it. In some embodiments, the method may further comprise the step of selecting only a portion of the nonwoven web or film for treating the fabric article. For example, if only one fabric care article is to be treated, a portion of the nonwoven web or film can be cut or cut and placed on or adhered to the fabric, or placed in water to form a relatively small amount of wash liquor, which can then be used to pretreat the fabric. In this way, the user can customize the fabric treatment process to the task at hand. In some embodiments, at least a portion of the nonwoven web or film may be applied to a fabric to be treated using the device. Exemplary devices include, but are not limited to, brushes and sponges. Any one or more of the foregoing steps may be repeated to achieve the desired fabric treatment benefits.

Method for preparing a fibrous structure

The following methods were used to form inventive examples 1-8 described herein. The fiber structure may be formed by means of a small device (a schematic of which is shown in fig. 7). The pressurized tanks suitable for batch operation are filled with material suitable for spinning. The pump used isPEP type II, having a capacity of 5.0 cubic centimeters per revolution (cc/rev), is manufactured by Parker Hannifin Corporation, Zenith Pumps division, of Sanford (N.C., USA). The material flow to the die is controlled by adjusting the revolutions per minute (rpm) of the pump. A tube connecting trough, a pump and a mold.

The die in fig. 8 has rows of circular extrusion nozzles (fig. 8) spaced from each other at a pitch P of about 1.524 millimeters (about 0.060 inches). The nozzle had a single inner diameter of about 0.305 millimeters (about 0.012 inches) and a single outer diameter of about 0.813 millimeters (about 0.032 inches). Each individual nozzle is surrounded by an annular and divergent widening orifice to provide an extraction air to each individual melt capillary. The material extruded through the nozzle is surrounded and elongated by a generally cylindrical flow of humid air supplied through an orifice.

The extraction air may be provided by heating compressed air from a source with a resistive heater, such as a heater manufactured by chromomax, Division of emerson Electric of Pittsburgh (Pa., USA). An appropriate amount of air flow is added to saturate or nearly saturate the heated air under electrically heated, thermostatically controlled transfer tube conditions. The condensate is removed in an electrically heated, thermostatically controlled separator.

The embryonic fibers are dried with a stream of drying air having a temperature of about 149 ℃ (about 300 ° f) to about 315 ℃ (about 600 ° f) provided by an electrical resistance heater (not shown) through a drying nozzle and discharged at an angle of about 90 degrees relative to the general direction of the extruded non-thermoplastic embryonic fibers. The dried embryonic fibers are collected on a collection device, such as a movable porous belt or molding member. The addition of a vacuum source directly below the forming zone can be used to help collect the fibers.

Table 1 below shows examples of filament-forming compositions for making filaments and/or fibrous structures suitable for use as laundry detergents. The mixture was prepared and placed in the pressurized tank in fig. 8.

TABLE 1

¹Celvol 523, Celanese/Sekisui, molecular weight 85,000-

The dried embryonic filaments can be collected on the molding member as described above. Due to the inherent configuration, the configuration of the molding member will provide a region that is air permeable. The filaments used to construct the molding member will be impermeable, while the interstitial regions between the filaments will be permeable. In addition, a pattern may be applied to the molding member to provide additional impermeable areas that may be continuous, discontinuous, or semi-continuous in nature. The vacuum used at the lay-up point is used to help deflect the fibers into the existing pattern. An example of one of these molding members is shown in fig. 9.

The base spinning conditions are achieved by collecting the web on a collecting molding member. These were passed under a mold and samples were collected after vacuum. The process was repeated and samples were collected with eight molding members of different designs. Representative pictures of the molding member and resulting fibrous structure are shown in fig. 10 (e.g., inventive examples 1-8 described herein). These fibrous structures may then be further processed.

Methods of forming fibrous structures are also described in U.S. Pat. No. 4,637,859.

In addition to the techniques described herein for forming regions in a fibrous structure having different properties (e.g., average density), other techniques may be applied to provide suitable results. One such example includes embossing techniques for forming such regions. Suitable stamping techniques are described in U.S. patent application publications 2010/0297377, 2010/0295213, 2010/0295206, 2010/0028621, and 2006/0278355.

Test method

Unless otherwise indicated, all tests described herein (including those described in the definitions section and test methods below) were performed on samples that had been conditioned at a temperature of 23 ℃ ± 1 ℃ and a relative humidity of 50% ± 2% for a minimum of 2 hours prior to testing. All tests were performed under the same environmental conditions. Samples with defects such as wrinkles, tears, holes, etc. were not tested. Samples conditioned as described herein are considered dry samples (e.g., "dry filaments") for the stated purpose. Furthermore, all tests were performed in a conditioning chamber.

Basis weight test method

Basis weight of the nonwoven structure and/or the dissolved fibrous structure was measured on a stack of twelve available units using a top-loading analytical balance with a resolution of ± 0.001 g. The balance uses an airflow hood to protect it from airflow and other disturbances. Precision cutting dies (measuring 3.500in + -0.0035 in by 3.500in + -0.0035 in) were used to prepare all samples.

The sample was cut into squares using a precision cut die. The cut squares were combined into a stack that was twelve samples thick. The mass of the sample stack was measured and the results recorded to the nearest 0.001 g.

Basis weight in lbs/3000ft²Or g/m²In units, as follows:

basis weight ═ mass of stack/[ (area of 1 square in stack) × (number of squares in stack) ]

For example,

basis weight (lbs/3000 ft)²) [ [ mass (g) of stacked body)/453.6 (g/lbs)]/[12.25(in²)/144(in²/ft²)×12]]×3000

Or,

basis weight (g/m)²) Mass of stack (g)/[79.032 (cm)/[²)/10,000(cm²/m²)×12]

The recorded result is accurate to 0.1lbs/3000ft²Or 0.1g/m². Sample size can be varied or varied using a precision cutter similar to that mentioned above so that the sample area in the stack is at least 100 square inches.

Water Content testing Method (Water Content Test Method)

The Water (moisture) Content present in the filaments, and/or fibers, and/or nonwoven web was tested using the Water Content Test Method.

The filaments and/or nonwoven fabric or parts thereof ("samples") were placed in a conditioning chamber in the form of pre-cut pieces at a temperature of 23 ℃ ± 1 ℃ and a relative humidity of 50% ± 2% for at least 24 hours prior to testing. Each sample has an area of at least 4 square inches, but is small enough in size to fit properly on a balance weighing pan. Under the temperature and humidity conditions mentioned above, the weight of the sample was recorded every five minutes using a balance with at least a four decimal places until a change of less than 0.5% of the previous weight was detected within a period of 10 minutes. The final weight was recorded as the "balance weight". The samples were placed in a forced air oven at 70 ℃. + -. 2 ℃ and 4%. + -. 2% relative humidity over 10 minutes and dried on top of the foil for 24 hours. After drying for 24 hours, the sample was removed and weighed within 15 seconds. This weight is expressed as the "dry weight" of the sample.

The water (moisture) content of the sample was calculated as follows:

the% water (moisture) in the 3 replicate samples was averaged to provide the% water (moisture) in the reported sample. The results were recorded to the nearest 0.1%.

Dissolution test method

Devices and materials (see also FIGS. 11 and 12)：

600mL beaker 240

Magnetic stirrer 250(Labline No.1250 type or equivalent)

Magnetic stirring rod 260(5cm)

Thermometer (1 to 100 ℃ C. +/-1 ℃ C.)

Cutting die- -stainless steel cutting die with dimensions of 3.8cm by 3.2cm

Timer (0-3,600 seconds or 1 hour) accurate to seconds. If the sample exhibits a dissolution time of greater than 3,600 seconds, the timer used should have a sufficient total time measurement range. However, the timer needs to be accurate to seconds.

Polaroid 35mm sliding bezel 270 (commercially available or equivalent from Polaroid Corporation)

35mm slide frame holder 280 (or equivalent)

Cincinnati, water or equivalent, having the following properties: total hardness of 155mg/L as CaCO₃Counting; the content of calcium is 33.2 mg/L; the magnesium content is 17.5 mg/L; the phosphate content was 0.0462.

Test protocol

The samples were equilibrated for at least 2 hours in a constant temperature and humidity environment of 23 ℃. + -. 1 ℃ and 50% RH. + -. 2%.

The basis weight of the samples was measured using the basis weight method defined herein.

Three dissolution test samples were cut from the nonwoven structure sample using a cutting die (3.8cm x 3.2cm) so that they fit in a 35mm slide frame 270 having an open area size of 24 x 36 mm.

Each sample was mounted in a separate 35mm slide frame 270.

A magnetic stir bar 260 was placed in a 600mL beaker 240.

Tap water flow (or equivalent) is turned on and the temperature of the water is measured with a thermometer and, if necessary, hot or cold water is adjusted to maintain it at the test temperature. The test temperature is 15 ℃. + -. 1 ℃ water. Once at the test temperature, beaker 240 is filled with 500mL + -5 mL of 15 deg.C + -1 deg.C tap water.

The entire beaker 240 was placed on a magnetic stirrer 250, the stirrer 250 was turned on, and the stirring speed was adjusted until a vortex was formed with the bottom of the vortex at the 400mL mark of the beaker 240.

The 35mm slide frame 270 is secured in the spring clips 281 of the 35mm slide frame holder 280 such that the long end 271 of the slide frame 270 is parallel to the water surface. The spring clip 281 should be positioned in the middle of the long end 271 of the slider frame 270. The depth adjuster 285 of the clip 280 should be set so that the distance between the bottom of the depth adjuster 285 and the bottom of the spring clip 281 is 11+/-0.125 inches. This configuration will position the sample surface perpendicular to the water flow direction. A slightly modified example of the arrangement of the 35mm slide frame and slide frame holder is shown in figures 1-3 of us patent 6,787,512.

In one movement, the fixed slide and clamp are dropped into the water and a timer is started. The sample was dropped so that the sample was located in the center of the beaker. Disintegration occurs when the nonwoven structure breaks. This was recorded as disintegration time. When all visible nonwoven structures were released from the slide frame, the slide frame was raised out of the water while continuing to monitor the solution of undissolved nonwoven structure fragments. Dissolution occurs when all nonwoven structural segments are no longer visible. This was recorded as the dissolution time.

Each sample was run in triplicate and the average disintegration and dissolution times were recorded. The average disintegration and dissolution times are in seconds.

The average disintegration and dissolution times are normalized to basis weight by dividing each by the sample basis weight as determined by the basis weight method defined herein. Disintegration and dissolution times normalized by basis weight in seconds per gsm sample (s/(g/m)²) In units of).

Average density test method

The fibrous structure may comprise a network of regions and a plurality of discrete regions having a characteristic density. A cross-sectional SEM micrograph of such a fibrous structure is shown in fig. 13. Regions of the fibrous structure are shown in the photomicrograph by including regions of different thicknesses. These thickness differences are one of the factors that contribute to the superior performance characteristics of these fibrous structures.

The regions of higher thickness have a lower structural density and these are often referred to as "pillows". The density of structures is higher in the areas with lower thickness and these are often referred to as "protrusions".

The areal density within the fibrous structure is determined by first treating a razor blade such as that available from Ted Pella Inc with a previously unused single-sided PTFEThe razor blade cuts a length of at least 2-3 projections and pillow areas. Each razor blade makes only one cut. Each cross-sectional sample was mounted on an SEM sample holder, fixed with a carbon paste, then inserted and frozen in liquid nitrogen. The samples were then transferred to an SEM chamber at-90 ℃, coated with gold/palladium for 60 seconds, and analyzed using a commercially available SEM equipped with a freezing system such as Hitachi S-4700 and Alto freezing systems and PCI (passive capture imaging) software for image analysis or equivalent SEM systems and equivalent software. All samples were evaluated in a scanning electron microscope while being frozen under vacuum to ensure their initial size and shape.

Pillow and protrusion thicknesses or network area and discrete area thicknesses were determined using image analysis software associated with the SEM equipment. Since the measurement is the thickness of the sample, such analysis software is standard for all SEM equipment. The measurement is performed with the thickness of the region or zone at its corresponding local maximum. The thickness values of at least 2 individual separate network regions (or discrete areas) are recorded and then averaged and recorded as the average network region thickness. The average thickness is measured in microns.

Independently, the basis weight of the sample measured for density is determined using the basis weight method defined herein. In gsm (g/m)²) Basis weight is calculated for the unit measurement using the basis weight method and used to calculate the areal density.

The following is a calculated basis weight of 100g/m²For the average network density and average discrete region density of the sample of (1), the network region average thickness is 625 microns and the discrete region average thickness is 311 microns.

Diameter testing method

The diameter of the discontinuous filaments or filaments within the nonwoven web or film is determined by using a Scanning Electron Microscope (SEM) or optical microscope and image analysis software. A magnification of 10,000 times 200 was chosen so that the filaments were suitably magnified for measurement. When SEM is used, these samples are sputtered with gold or palladium compounds to avoid charging and vibration of the filaments in the electron beam. A manual program to determine long filament diameter is used from images (on a monitor screen) taken with SEM or optical microscope. Using a mouse and cursor tool, the edge of the randomly selected filament is searched for and then measured across its width (i.e., the direction of the filament perpendicular to the point) to the other edge of the filament. The scaling image analysis tool provides scaling to obtain the actual reading in μm. For filaments within the nonwoven web or film, a plurality of filaments across a sample of the nonwoven web or film are randomly selected using SEM or optical microscopy. At least two portions of the nonwoven web or film (or web on the inside of the product) are cut and tested in this way. A total of at least 100 such measurements were made and all data were recorded for statistical analysis. The data recorded were used to calculate the mean value of the filament diameters, the standard deviation of the filament diameters and the median value of the filament diameters.

Another useful statistic is to calculate the population number of filaments below a certain upper limit. To determine this statistic, the software was programmed to count how many filament diameters were below an upper limit of the result, and the number (divided by the total number of data and multiplied by 100%) was reported as a percentage below the upper limit, e.g., a percentage below 1 micron diameter or% -submicron. We represent the measured diameter (in μm) of a single round filament as di.

If the filaments have a non-circular cross-section, the measurement of the filament diameter is determined and set equal to the hydraulic diameter, which is four times the cross-sectional area of the filament divided by the circumference of the cross-section of the filament (the outer circumference in the case of hollow filaments). The number average diameter, or average diameter, is calculated as follows:

tensile test method: elongation, tensile Strength, TEA and modulus

Elongation, tensile strength, TEA and tangent modulus were measured on a constant-rate extension tensile tester (a suitable Instrument is available from Thwing-Albert Instrument Co. (Wet Berlin, NJ) EJA Vantage) with a computer interface using a load cell for which the measured force is within 10% to 90% of the sensor limit. Both the movable (upper) and fixed (lower) pneumatic grips were fitted with stainless steel smooth grips, 25.4mm high and wider than the width of the specimen. Air pressure of about 60psi was supplied to the fixture.

Eight available units of nonwoven structure and/or dissolved fibrous structure were divided into two stacks of four samples each. The samples in each stack were consistently oriented with respect to the Machine Direction (MD) and Cross Direction (CD). One of the stacks was designated for testing in the machine direction and the other in the cross direction. A one inch precision cutter (Thwing AlbertJDC-1-10 or the like) was used to cut 4 longitudinal strips from one stack and 4 transverse strips from the other, with dimensions of 1.00in + -0.01 in wide by 3.0-4.0 in long. Each bar of one available unit thickness will be considered a single sample for testing.

The tensile tester was programmed to perform an extension test, collecting force and extension data at a collection rate of 20Hz, during which the chuck was raised at a rate of 2.00in/min (5.08cm/min) until the sample broke. The fracture sensitivity was set at 80%, i.e. the test was terminated when the measured force dropped to 20% of the maximum peak force, after which the collet was returned to its original position.

The gauge length was set to 1.00 inch. The chuck and load cell are zeroed. A single sample of at least 1.0in is inserted into the upper clamp, aligned vertically in the upper and lower clamps, and the upper clamp is closed. A single sample is inserted in the lower clamp and closed. The single sample should be subjected to sufficient tension to eliminate any slack, but less than 5.0g of force on the load cell. The tensile tester was started and data collection was started. Repeat testing was performed in a similar manner for all four longitudinal and four transverse single samples.

The software was programmed to calculate from the constructed force (g) versus extension (in) curve as follows:

tensile strength is the maximum peak force (g) divided by the sample width (in) and is reported in g/in to the nearest 1 g/in.

The adjusted gauge length was calculated as the extension measured when 3.0g force (in) was added to the initial gauge length (in).

Elongation was calculated as the extension at maximum peak force (in) divided by the adjusted gauge length (in) multiplied by 100 and reported as% to the nearest 0.1%.

The Total Energy (TEA) was calculated as the area under the force curve (g in) extending from zero to the extended integral at the maximum peak force, divided by the product of the adjusted gauge length (in) and the sample width (in), and recorded to 1g in/in²。

The force (g) versus extension (in) curve is redrawn as a force (g) versus strain curve. Strain is defined herein as the extension (in) divided by the adjusted gauge length (in).

The software was programmed to calculate from the constructed force (g) versus strain curve as follows:

the tangent modulus was calculated as the slope of a linear line drawn between two data points of the force (g) versus strain curve, where one of the data points used was the first data point recorded after 28g of force and the other data point used was the first data point recorded after 48g of force. The slope was then divided by the sample width (2.54cm) and recorded to the nearest 1 g/cm.

The tensile strength (g/in), elongation (%), total energy (g in/in) were calculated for four transverse single samples and four longitudinal single samples²) And a tangent modulus (g/cm). The calculation is the average of each individual parameter for the transverse and longitudinal samples.

Computing：

Geometric mean tension (square root of [ tensile strength in the machine direction (g/in) × tensile strength in the transverse direction (g/in) ]

Geometric mean peak elongation (square root of [ longitudinal elongation (%) × transverse elongation (%) ]

Geometric mean TEA ═ longitudinal TEA (g in/in)²) Xtransverse TEA (g in/in)²)]Square root of

Geometric mean modulus (square root of [ longitudinal modulus (g/cm) × transverse modulus (g/cm) ]

Total Dry Tensile (TDT) longitudinal tensile (g/in) + transverse tensile (g/in)

Total TEA ═ longitudinal TEA (g × in/in)²) + transverse TEA (g in/in)²)

Total modulus ═ longitudinal modulus (g/cm) + transverse modulus (g/cm)

Tensile ratio (g/in) tensile strength in machine direction (g/in)/tensile strength in transverse direction (g/in)

Topographical feature measurement of different density fibrous structures

Topographical measurements of different density fiber structures were obtained via computer-controlled edge projection optical profilometry. An optical profilometer system measures the physical dimensions of a test surface, producing a map of surface height (z) versus side displacement in the x-y plane. A suitable optical profilometer instrument will have a field of view and x-y resolution such that the acquired image has at least 10 pixels linearly across the narrowest feature being measured. A suitable instrument is the GFM Mikrocad system or equivalent, running the ODSCAD software version 4 or 6, available from GFMessthechnik GmbH (Teltow, Germany).

If desired, in order for the sample to properly reflect an accurate measurement of the surface structure, the surface to be measured is lightly sprayed with a spray of very fine white powder. Preferably, the sprayer is NORD-TEST Developer U89, available from Helling GmbH (Heidgraben, Germany), which is sold for detecting cracks in metal objects and welds. Shortly before applying this spray, the samples should equilibrate at 23 ℃ ± 2 ℃ and 50% ± 2% relative humidity for at least 2 hours, and after spraying for at least 2 hours. Care was taken to deposit only the minimum amount of white spray needed to produce a thin reflective white coating.

The sample should be equilibrated for at least 2 hours at 23 ℃. + -. 2 ℃ and 50%. + -. 2% relative humidity shortly before the measurement is taken.

The area of the fibrous structure to be measured is limited to areas with regions of different density and does not include other areas or regions that may be present. The sample was placed so that the surface with the measurements faced up, under the projection head of the profilometer and perpendicular to it. According to the instructions of the device manufacturer and according to the manufacturer's overview to achieve optimized illumination and reflection requirements. Digital images are captured and saved.

Any part of the image that is not part of the area to be measured should be cut out from the captured image. Such cropping must be done prior to any further image processing, filtering or measurement analysis. The size of the resulting cropped image may vary from sample to image depending on the size of the patterned area of the sample.

The images may be processed in the instrument software prior to taking the measurements to smooth noise in the images somewhat and reduce irregularities and fluctuations due to the overall shape of the sample. The noise filtering process includes removing invalid pixel values (those black pixels having a gray value at the black limit of the gray scale range) and removing sharp or anomalous peaks (those very bright pixels identified by the software as statistical outliers). A polynomial high pass filter is then utilized with the following settings: n is 8, the difference. For samples with very small features, it may be useful to additionally use a fourier filter (e.g., 5mm wave filter, fine structure results) in cases where it is difficult to clearly observe the pattern features. When used, the Fourier filter removes features larger than the filter length as noise and thus reduces the ripple, reducing the statistical standard deviation around the topographical feature measurements. It is therefore important that the size of the filter used be larger than any structure of interest in order not to filter out the features. The processed image, such as the topographical feature image shown in fig. 14, can be displayed, analyzed, and measured. Fig. 14 is then cropped and flattened via filtering with a polynomial (n-8 difference) filter to remove irregularities due to the overall fluctuation of the sample.

Measurements are then made from the processed topographical feature images to obtain the spatial parameter height difference (E) and transition region width (T). These measurements are performed using the instrument software to map straight line regions of interest within the topographical images of the x-y surface of the sample, and then to generate height profiles along these straight lines. The rectilinear regions of interest are drawn such that they span the centers of the continuous region and the adjacent discrete regions, sampling a number of different locations within each image. The lines are drawn such that they bisect each transition region between the continuous region and the discrete region at an angle perpendicular to the long axis of the transition region, as shown in fig. 15. As shown in fig. 15, a series of rectilinear regions of interest are drawn across the continuous and discrete zones, bisecting each transition region at an angle perpendicular to the long axis of the transition region. The parameters (E) and (T) are then measured from the height profiles generated from these straight regions of interest.

In the height profile, the x-axis of the graph represents the length of the line and the y-axis represents the vertical height of the surface perpendicular to the plane of the sample. The height difference (E) was measured in a micrometer as the vertical straight-line distance from the peak top to the lowest point of the adjacent depression on the height profile shown in fig. 16. As shown in fig. 16, a height profile plot along a straight line region of interest from a topographical feature image shows a plurality of height difference (E) measurements. Typically, this represents the maximum vertical height difference between a continuous region and an adjacent discrete region, or vice versa. The transition zone width (T) is measured in the micrometer as the x-axis width of the curve across the center sixty percent (60%) of the height difference (E) on the height profile as shown in fig. 17. As shown in fig. 17, the height profile plotted by the topographical feature image along the straight line region of interest shows a plurality of transition region widths (T). Generally, this represents the rate of transition from a continuous region to an adjacent discrete region, or vice versa.

Where samples have discrete regions that appear to be divided into two or more discrete types, their overall shape, size, height and density are determined, e.g., by visual inspection, and the independent (E) and (T) values are determined for each discrete region type and paired contiguous region.

If the sample apparently exhibits a pattern with more than one discrete area at different locations in the product, each pattern will have (E) and (T) values determined independently of one or more other patterns.

If the sample has a first region and an adjacent second region that appear significantly different in their surface height, the product will have (E) and (T) values measured from these regions. In this case, all the methods given herein will be described and the first region and the second region replace both the continuous region and the discrete region described in the methods.

For each pattern to be tested, five parallel-measured product samples are imaged, and the measurement from each parallel-measured sample consists of at least ten height differences (E) per discrete zone type and ten transition zone widths (T) per discrete zone type. This process was repeated for each plane of each sample. The (E) and (T) values from the plane with the maximum value of (E) are recorded. For each parameter calculated for a particular pattern and discrete region type, the values from each of the five replicate samples were averaged together to obtain a final value for each parameter.

Examples of the invention

Examples 1-8 of the present invention are provided below. As shown, the average thickness and average density of the network regions and discrete regions may vary. Additionally shown, inventive example 2 illustrates a sample having multiple regions and provides an average thickness and average density for each of these regions.

The machine direction tensile strength, machine direction peak elongation, machine direction TEA and machine direction modulus values for inventive examples 3,4 and 8 are provided below.

Examples of the invention	Basis weight	Thickness of	Longitudinal tensile strength	Longitudinal peak elongation	Longitudinal TEA	Longitudinal modulus
								gsm	Micron meter	g/in	％	g*in/in²	g/cm
3	94.7	463.7	644	64.1	318	2302
							4	108.7	477.5	688	68.5	372	2793
8	86.6	417.8	636	65.2	324	3017

The tensile strength in the transverse direction, peak elongation in the transverse direction, TEA in the transverse direction, and modulus values in the transverse direction of inventive examples 3,4, and 8 are provided below.

Examples of the invention	Basis weight	Thickness of	Longitudinal tensile strength	Longitudinal peak elongation	Longitudinal TEA	Longitudinal modulus
								gsm	Micron meter	g/in	％	g*in/in²	g/cm
3	94.7	463.7	579	84.2	359	1059
							4	108.7	477.5	629	74.2	362	1853
8	86.6	417.8	589	83.7	376	2305

The geometric mean tensile strength, geometric peak elongation, geometric mean TEA, and geometric mean modulus values for inventive examples 3,4, and 8 are provided below.

Profile data relating to examples 1-8 of the present invention, including, for example, height differences (E) and transition zone widths (T), are provided below.

The following provides water content data for inventive examples 2,3 and 8.

Examples of the invention	Water content (%)
		2	7.5
3	8.1
		8	7.5

The dissolution times and disintegration times for inventive examples 2-4 and 8 are provided below according to the dissolution test methods described herein.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each of the above dimensions is intended to represent the recited value and the functionally equivalent range surrounding that value. For example, the disclosed dimension "40 mm" is intended to mean "about 40 mm".

For clarity, the total "% by weight" value does not exceed 100% by weight.

Each document cited herein, including any cross-referenced or related patent or patent application, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A fibrous structure comprising filaments wherein at least one of the filaments comprises one or more filament-forming materials present in the filament in a total amount of less than 80% by weight on a dry filament basis and one or more active agents that are releasable from the filament upon exposure to conditions of intended use in an amount of greater than 20% by weight on a dry filament basis, wherein the one or more filament-forming materials comprise a water-soluble hydroxyl polymer, wherein the intended use is hair care of the hair, the fibrous structure further comprising:

(a) a continuous network region, wherein the network region comprises a first average density; and

(b) a plurality of discrete regions comprising a second average density, wherein the discrete regions are dispersed throughout the network region, and wherein the first average density and the second average density are different.

2. The fibrous structure according to claim 1 wherein the first average density is from 0.05g/cc to 0.80 g/cc.

3. The fibrous structure according to claim 1 or 2 wherein the second average density is from 0.05g/cc to 0.80 g/cc.

4. The fibrous structure according to claim 1 wherein the continuous network region is a macroscopically monoplanar, patterned continuous network region.

5. The fibrous structure according to claim 1 wherein the water-soluble hydroxyl polymer is selected from the group consisting of: polyvinyl alcohol, carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol, and mixtures thereof.

6. The fibrous structure according to claim 1 exhibiting a basis weight of 1500gsm or less.

7. The fibrous structure according to claim 1 wherein the one or more active agents comprises a surfactant.

8. The fibrous structure according to claim 1 wherein at least one of the one or more active agents is a fabric care agent.

9. The fibrous structure according to claim 1 wherein the fibrous structure comprises two or more different active agents.

10. The fibrous structure according to claim 1 wherein the fibrous structure further comprises a dissolution aid.

11. The fibrous structure according to claim 1 exhibiting a water content of from 0% to 20%.

12. The fibrous structure according to claim 1 wherein at least some of the filaments exhibit a diameter of less than 50 μ ι η.

13. A method of treating a fabric article in need of treatment, the method comprising the step of treating the fabric article with the fibrous structure according to any of the preceding claims.

14. The method of claim 13, wherein the processing step comprises one or more steps selected from the group consisting of:

(a) pretreating the fabric article prior to washing the fabric article;

(b) contacting the fabric article with a wash liquor formed from a nonwoven web and water;

(c) contacting the fabric article with the nonwoven web in a dryer;

(d) drying the fabric article in the presence of the nonwoven web in a dryer; and

(e) combinations thereof.